TW200932709A - Benzophenanthrene derivative and organic electroluminescent device employing the same - Google Patents
Benzophenanthrene derivative and organic electroluminescent device employing the same Download PDFInfo
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Abstract
Description
200932709 六、發明說明: [發明所屬之技術領城] 技術領域 本發明係有關於可作為有機電致發光元件用材料之新 5 ❿ 10 15 ❿ 20 穎縮合芳香環衍生物(苯并菲衍生物)、及使用其之有機電致 發光元件。 背景技術 有機電致發光元件(以下將電致發光略稱為EL)係利用 藉由施加電場所造成之從陽極注入的電洞與從陰極注入的 電子之再結合能量,使發光材料之螢光性物質發光之原理 的自行發光元件。 有機EL元件的進步是顯著的,又,有機EL元件因具有 低施加電壓驅動性、高亮度、發光波長多樣性、高速應答 性、可製作為薄型輕量之發光裝置特徵,預期可適用於 廣泛用途。 有機EL元件所使㈣發光材料由於會大_#元件發 光顏色及發光壽命,因此自以往已積極研究。 " 發光材料,已知有例如,三(8_經基㈣)紹錯合物等餐 合錯合物、香豆靈(coumalin)衍生物、四苯美 一, 土 丁一-辦^衍生 物、雙細(bisstyryla咖e)衍生物”号二唾衍生 材料。藉由該等發光材料,可得藍色 “ 的發光。 色至紅色之可見光領域 又 ,已對於使用填光性化合物作為發光材料, 且使用 3 200932709 三重態能量來發光等進行研究。例如,使用銀錯合物作為 發光材料之有機EL元件已知可顯現高發光效率。 又’使用聚苯基乙烯(PPV)作為共概系高分子之有機虹 元件是已知的。於該^件中塗布ppv且成膜成單層並確認 5 發光。 專利文獻1揭示了使用含有9,10_二_(2_萘基)葱衍生物 之層作為有機層,專利文獻2及3中揭示了使用含有菲衍生 物之層作為發光層。 專利文獻1 :美國專利第5935721號說明書 10 專利文獻2 ·美國專利申請公開第2004/076853號說明 書 專利文獻3 :特開2006-151844號公報 本發明之目的係提供一種適合作為有機EL元件用材料 之有機材料。 15【發明内容】 發明揭示 本發明人著重於以苯并菲衍生物作為有機EL元件用材 料,而致力進行研究。結果,發現具有預定構造之苯并菲 衍生物對於有機EL元件的長壽命化、高效率及低電壓化有 20 貢獻,而完成本發明。 依據本發明,可提供以下之縮合芳香環衍生物等。 1. 一種下述式(1)表示之縮合芳香環衍生物。 200932709200932709 VI. Description of the Invention: [Technology of the Invention] The present invention relates to a novel 5 ❿ 10 15 ❿ 20 condensed aromatic ring derivative (benzophenanthrene derivative) which can be used as a material for an organic electroluminescence device. ), and organic electroluminescent elements using the same. BACKGROUND ART An organic electroluminescence element (hereinafter, electroluminescence is abbreviated as EL) is a method of fluorescing a luminescent material by utilizing a recombination energy of a hole injected from an anode and an electron injected from a cathode by applying an electric field. A self-luminous component that illuminates the substance. The progress of the organic EL element is remarkable, and the organic EL element is expected to be applicable to a wide range of light-emitting devices because of its low applied voltage driving property, high luminance, illuminating wavelength diversity, high-speed responsiveness, and the ability to be made thin and lightweight. use. The (IV) luminescent material of the organic EL element has been actively studied since it has a large _# component luminescent color and luminescent lifetime. " Luminescent materials, such as, for example, three (8-trans-based (tetra)) succinct complexes, coumalin derivatives, tetraphenyl methacrylate, diced A double-salt-derived material of the product, a double-bis(bisstyryla) derivative. With these luminescent materials, a blue "luminescence" is obtained. The color-to-red visible light field has been studied by using a light-filling compound as a light-emitting material and using 3 200932709 triplet energy to emit light. For example, an organic EL element using a silver complex as a light-emitting material is known to exhibit high luminous efficiency. Further, an organic rainbow element using polyphenylethylene (PPV) as a co-polymer is known. The ppv was applied to the film and formed into a single layer and confirmed to emit light. Patent Document 1 discloses the use of a layer containing a 9,10-di-(2-naphthyl) onion derivative as an organic layer, and Patent Documents 2 and 3 disclose the use of a layer containing a phenanthrene derivative as a light-emitting layer. Patent Document 1: U.S. Patent No. 5,935, 721, the disclosure of which is incorporated herein by reference. Organic material. [Explanation] The present inventors focused on the use of a benzophenanthrene derivative as a material for an organic EL device, and made efforts to carry out research. As a result, it has been found that a benzophenanthrene derivative having a predetermined structure contributes 20 to the long life, high efficiency, and low voltage of the organic EL device, and the present invention has been completed. According to the invention, the following condensed aromatic ring derivatives and the like can be provided. A condensed aromatic ring derivative represented by the following formula (1). 200932709
5 10 (式中,Ra、Rb各自獨立表示氫原子或取代基;ρ表示 1〜8之整數、q表示1〜11之整數;當ρ為2以上時,複數1^可 各自相同或相異,且亦可以鄰接之複數Ra形成環;當q為2 以上時,複數Rb可各自相同或相異;L!係單鍵、取代或無 取代之2價連結基;ΑΓι表示取代或無取代之核碳數6〜50的 芳基、或者核原子數5〜50之取代或無取代的雜芳基。但, L!之取代基、Ar!之取代基、Ra&Rb未包含取代或無取代之 胺基)。 2.如1之縮合芳香環衍生物,係下述式(2)表示者。5 10 (wherein, Ra and Rb each independently represent a hydrogen atom or a substituent; ρ represents an integer of 1 to 8, and q represents an integer of 1 to 11; and when ρ is 2 or more, plural 1^ may be the same or different And may also form a ring by a plurality of adjacent Ra; when q is 2 or more, the plural Rb may be the same or different; L! is a single bond, a substituted or unsubstituted divalent linking group; ΑΓι means a substituted or unsubstituted An aryl group having 6 to 50 nucleus or a substituted or unsubstituted heteroaryl group having 5 to 50 nucleus. However, the substituent of L!, the substituent of Ar!, and Ra&Rb do not contain a substitution or an unsubstituted. Amino group). 2. The condensed aromatic ring derivative of 1, which is represented by the following formula (2).
❿ (式中,Ra、Rb、Aq、p及q與式⑴相同)。 3. 如1或2之縮合芳香環衍生物,其中Ar!係取代或無取 代之核碳數10〜20的縮合芳香族環基。 4. 如1之縮合芳香環衍生物,係下述式(3)表示者。 200932709❿ (wherein, Ra, Rb, Aq, p, and q are the same as in the formula (1)). 3. A condensed aromatic ring derivative according to 1 or 2, wherein Ar! is substituted or unsubstituted condensed aromatic ring group having a core carbon number of 10 to 20. 4. The condensed aromatic ring derivative of 1, which is represented by the following formula (3). 200932709
(式中,Ra、Rb、p及q與式(1)相同;心各自獨立表示氫 原子或取代基;r表示1〜4之整數;當r為2以上時,複數Rc 可各自相同或相異,且亦可以鄰接之複數Rc形成環;Ar2表 5 示取代或無取代之核碳數6〜50的芳基。但,Ar2之取代基及(wherein, Ra, Rb, p and q are the same as in the formula (1); the cores each independently represent a hydrogen atom or a substituent; r represents an integer of 1 to 4; and when r is 2 or more, the plural Rc may be the same or each And may also be adjacent to the plural Rc to form a ring; Ar2 Table 5 shows a substituted or unsubstituted aryl group having a core carbon number of 6 to 50. However, the substituent of Ar2 and
Rc未包含取代或無取代之胺基)。 5. 如4之縮合芳香環衍生物,其中Ar2係取代或無取代之 核碳數10〜20的縮合芳香族環基。 6. 如1之縮合芳香環衍生物,係下述式(4)表示者。 10 [化 4]Rc does not contain a substituted or unsubstituted amine group). 5. A condensed aromatic ring derivative according to 4, wherein the Ar2 is a substituted or unsubstituted fused aromatic ring group having a core carbon number of 10 to 20. 6. The condensed aromatic ring derivative of 1, which is represented by the following formula (4). 10 [Chem. 4]
(式中,Ra、Rb、p及q與式(1)相同;Rc、Rd各自獨立表 示氫原子或取代基;r表示1〜4之整數,s表示1〜4之整數; 當r為2以上時,複數Re可各自相同或相異;當s為2以上時, 15 複數Rd可各自相同或相異;Ar2表示取代或無取代之核碳數 6〜50的芳基。但,Ar2之取代基、Rc及Rd未包含取代或無取 代之胺基)。 200932709 7·如6之縮合芳香環衍生物,其中係取代或無取代之 核碳數10〜20的縮合芳香族環基。 8.如1之縮合芳香環衍生物,係下述式(5)表示者。 [化5](wherein, Ra, Rb, p and q are the same as in the formula (1); Rc and Rd each independently represent a hydrogen atom or a substituent; r represents an integer of 1 to 4, and s represents an integer of 1 to 4; when r is 2 In the above, the plural Re may be the same or different; when s is 2 or more, the 15 plural Rds may be the same or different; and Ar2 represents a substituted or unsubstituted aryl group having a core carbon number of 6 to 50. However, Ar2 The substituent, Rc and Rd do not contain a substituted or unsubstituted amine group). 200932709. The condensed aromatic ring derivative of 6, wherein the substituted or unsubstituted fused aromatic ring group having a core carbon number of 10 to 20 is used. 8. The condensed aromatic ring derivative according to 1, which is represented by the following formula (5). [Chemical 5]
(式中,Ra、Rb、ρ及q與式⑴相同;仏各自獨立表示氫 原子或取代基;s表示1〜4之整數;當8為2以上時,複數Rd - 可各自相同或相異;Ar3表示取代或無取代之核破數10〜50 的縮合芳香族環基。但,Ar3之取代基及Rd未包含取代或無 ' ίο 取代之胺基)。 - 9.如8之縮合芳香環衍生物,其中Ar3係取代或無取代之 萘基。 G ίο·—種有機電致發光元件用材料,其含有如1〜9中任 一項之縮合芳香環衍生物。 15 11.如10之有機電致發光元件用材料,其係發光材料。 12. —種有機電致發光元件,包含有:陽極與陰極;及 被挾持於前述陽極與陰極之間含發光層之1層以上的有 機薄膜層,前述有機薄膜層之至少1層係含有如申請專利範 圍第1〜9項中任一項之縮合芳香瓖衍生物。 13. 如12之有機電致發光元件,其中前述發光層含有前 7 20 200932709 述縮合芳香環衍生物。 14·如13之有機電致發光元件,其中前述縮合芳香環衍 生物係主體材料。 15·如12〜14中任一項之有機電致發光元件,其中前述 5 發光層更含有螢光性摻雜物及磷光性摻雜物之至少一者。 16·如15之有機電致發光元件,其中前述螢光性摻雜物 係芳胺化合物。 17.如15之有機電致發光元件,其中前述螢光性摻雜物 係苯乙烯胺化合物。 1〇 依據本發明,可提供適合作為有機EL元件用材料之縮 合芳香環衍生物。 使用本發明之縮合芳香環衍生物的有機EL元件係長壽 命且高效率,可低電壓驅動。 圖式簡單說明 15 帛1圖係本發明一實施形態之有機EL元件的概略載面 圖。 Γ實施方式] 實施發明之最佳形態 以下’具體地卿本發明之縮合料環衍生物。 物 本發明之縮合芳香環魅物係'下述式⑴表示之化合 且以下述式(2H5)表示之化合物的任— [化6] 20 (1) 200932709(wherein, Ra, Rb, ρ, and q are the same as those of the formula (1); 仏 each independently represents a hydrogen atom or a substituent; s represents an integer of 1 to 4; and when 8 is 2 or more, the plural Rd - may be the same or different Ar3 represents a substituted or unsubstituted nucleating group having 10 to 50 condensed aromatic ring groups. However, the substituent of Ar3 and Rd do not contain a substituted or unsubstituted amino group. A condensed aromatic ring derivative such as 8, wherein the Ar3 is a substituted or unsubstituted naphthyl group. A material for an organic electroluminescence device comprising the condensed aromatic ring derivative according to any one of 1 to 9. 15 11. A material for an organic electroluminescence device according to 10, which is a luminescent material. 12. An organic electroluminescence device comprising: an anode and a cathode; and an organic thin film layer supported by one or more layers of the light-emitting layer between the anode and the cathode, wherein at least one of the organic thin film layers contains A condensed aromatic hydrazine derivative according to any one of claims 1 to 9. 13. The organic electroluminescent device according to 12, wherein the luminescent layer comprises a condensed aromatic ring derivative as described in the previous paragraph 7 20 200932709. 14. The organic electroluminescent device according to 13, wherein the condensed aromatic ring derivative is a host material. The organic electroluminescence device according to any one of 12 to 14, wherein the luminescent layer further comprises at least one of a fluorescent dopant and a phosphorescent dopant. 16. The organic electroluminescent device according to 15, wherein the fluorescent dopant is an arylamine compound. 17. The organic electroluminescent device according to 15, wherein the fluorescent dopant is a styrylamine compound. 1〇 According to the present invention, a condensed aromatic ring derivative suitable as a material for an organic EL device can be provided. The organic EL device using the condensed aromatic ring derivative of the present invention has a long life and high efficiency, and can be driven at a low voltage. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic plan view of an organic EL device according to an embodiment of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the invention is hereinafter, specifically, the condensed ring derivative of the present invention. The condensed aromatic ring enchantment of the present invention is a compound represented by the following formula (1) and represented by the following formula (2H5) - [Chemical 6] 20 (1) 200932709
1~8之整數、q表示1〜11之整數;當p為2以上時,口表禾 久自相同或;te显,a τή: vr w违κ 4立a义仅说士 — a^T (式中,Ra、Rb各自獨立表示氫原子或取代基. 各自相同或相異,且亦可以鄰接之複數^形成壤;备 备ί 严 5 10 以上時,複數Rb可各自相同或相異;Ll係單鍵、取代或^ 取代之2價連結基;Ar!表示取代或無取代之核碳數6〜50的 方基、或者核原子數5〜50之取代或無取代的雜芳基。但, L!之取代基、Ar〗之取代基、心及心未包含取代或無取代之 胺基)。 [化7]An integer from 1 to 8, q represents an integer from 1 to 11; when p is 2 or more, the mouth table is long since the same or; te is significant, a τή: vr w violates κ 4 stands for a sense only - a^T (wherein, Ra and Rb each independently represent a hydrogen atom or a substituent. They are each the same or different, and may be adjacent to each other to form a soil; when the ruthenium 5 10 or more, the plural Rbs may be the same or different; Ll is a monovalent, substituted or substituted divalent linking group; Ar! represents a substituted or unsubstituted aryl group having 6 to 50 nucleus or a substituted or unsubstituted heteroaryl group having 5 to 50 nucleus. However, the substituent of L!, the substituent of Ar, the heart and the heart do not contain a substituted or unsubstituted amine group). [Chemistry 7]
φ 15Φ 15
(3) (式中,Ra、Rt P*q與式⑴相同,Rc各自獨立表示 氫 9 200932709 原子或取代基,r表示1〜4之整數。當r為2以上時,複數Rc 可各自相同或相異。Ar2表示取代或無取代之核碳數6〜50的 芳基。但,Ar2之取代基及1^未包含取代或無取代的胺基。) [化9](3) (wherein, Ra, Rt P*q are the same as formula (1), Rc each independently represents hydrogen 9 200932709 atom or a substituent, and r represents an integer of 1 to 4. When r is 2 or more, plural Rc may be the same Or different. Ar2 represents a substituted or unsubstituted aryl group having a core carbon number of 6 to 50. However, the substituent of Ar2 and 1^ do not contain a substituted or unsubstituted amine group.) [Chem. 9]
(式中,Ra、Rb、p及q與式⑴相同。Rc、Rd各自獨立表 示氫原子或取代基,r表示1〜4之整數,s表示1〜4之整數。 當r為2以上時,複數Rc可各自相同或相異。當s為2以上時, 複數Rd可各自相同或相異。Ar2表示取代或無取代之核碳數 10 6〜50的芳基。但,Ar2之取代基、Re&Rd未包含取代或無取 代之胺基。) [化 10](In the formula, Ra, Rb, p and q are the same as those in the formula (1). Rc and Rd each independently represent a hydrogen atom or a substituent, r represents an integer of 1 to 4, and s represents an integer of 1 to 4. When r is 2 or more The plural Rc may be the same or different. When s is 2 or more, the plural Rd may be the same or different. Ar2 represents a substituted or unsubstituted aryl group having a core carbon number of 10 6 to 50. However, the substituent of Ar2 Re&Rd does not contain a substituted or unsubstituted amine group.) [Chemical 10]
(式中,Ra、Rb、p及q與式⑴相同。心各自獨立表示氫 15 原子或取代基,s表示1〜4之整數。當s為2以上時,複數Rd 可各自相同或相異。Ar3表示取代或無取代之核碳數10〜50 10 200932709 的縮合芳錢縣。但,如之取似及包含取代或益 取代的胺基。) a Rb Rc&Rd表示之未包含取代或無取代的胺基之 取代基,可舉例如:燒基(以碳數!,為佳,較佳者是碳數 5 1〜12,特佳者為碳數1〜8,例如:甲基、乙基、異丙基、t_ 丁基、η-辛基、n_癸基、n十六燒基、環丙基、環戍基、環 己基等)、烯基(以碳數2〜20為佳,較佳者是碳數2〜12,特 Q 佳者為碳數2〜8,例如:乙婦基、丙烯基、2-丁稀基、3_戊 烯基等)、炔基(以碳數2〜20為佳,較佳者是碳數2〜12,特 10佳者為碳數2〜8’例如:丙块基、3_戊块基等)、取代或無取 代之芳基(以碳數6〜20為佳,特佳者為6〜14,例如··苯基、 蔡基、菲基、苐基),·取代基,可舉例如:芳基(以碳數G〜2〇 • 為佳,特佳者為6〜14,但未含有蔥骨架,例如··苯基、萘 基、菲基)、雜芳基(以碳數1〜30為佳,較佳者是碳數卜;^, 15例如:呋喃基、嘍吩基、苯并噚唑基、苯并噻唑基、苯并 〇 呋喃基、二苯并呋喃基、苯并硫苯基(benzothiophenyl)、二 笨并硫苯基(dibenzothiophenyl)等)、烷氧基(以碳數卜如 佳,較佳者是碳數丨〜以,特佳者為碳數卜8,例如:甲氧基、 乙氧基、丁氧基等。)、芳氧基(以碳數6〜2〇為佳,較佳者是 碳數6〜16,特佳者為碳數6〜12,例如:苯氧基、2_萘氧基 等)、醯基(以碳數1〜20為佳,較佳者是碳數卜^,特佳者 為碳數1〜12,例如:乙醯基、苯甲醯基、甲醯基、三甲基 乙酿基等)、烧氧基幾基(以碳數2〜2〇為佳,較佳者是碳數 2〜16,特佳者為碳數2〜12,例如··甲氧基羰基、乙氧基羰 11 200932709 5 10 15 20(wherein, Ra, Rb, p and q are the same as those of the formula (1). The cores each independently represent a hydrogen atom or a substituent, and s represents an integer of 1 to 4. When s is 2 or more, the plural Rds may be the same or different. Ar3 represents a substituted or unsubstituted nucleophilic carbon number of 10 to 50 10 200932709. However, it is similar and contains a substituted or a substituted amine group.) a Rb Rc&dd represents no substitution or The substituent of the unsubstituted amino group may, for example, be a calcination group (preferably, carbon number: preferably, the carbon number is 5 to 12, and particularly preferably the carbon number is 1 to 8, for example, methyl group, Ethyl, isopropyl, t-butyl, η-octyl, n-fluorenyl, nhexadecanyl, cyclopropyl, cyclodecyl, cyclohexyl, etc.), alkenyl (carbon number 2 to 20) Preferably, the carbon number is 2 to 12, and the specific Q is preferably a carbon number of 2 to 8, for example, an ethyl group, a propenyl group, a 2-butylenyl group, a 3-pentenyl group, etc., an alkynyl group. The carbon number is preferably from 2 to 20, preferably from 2 to 12 carbon atoms, particularly preferably from carbon 2 to 8', for example, a propyl group, a 3-pentyl group, etc., a substituted or unsubstituted aryl group. (It is better to have a carbon number of 6 to 20, and a particularly good one is 6 to 14, such as benzene. , Cai Ji, Fickey, thiol), · Substituents, for example, aryl (carbon number G ~ 2 〇 • is better, especially good for 6 to 14, but does not contain onion skeleton, for example ··· Phenyl, naphthyl, phenanthryl), heteroaryl (preferably having a carbon number of from 1 to 30, preferably carbon number; ^, 15 for example: furyl, porphinyl, benzoxazolyl, benzene And a thiazolyl group, a benzofuranyl group, a dibenzofuranyl group, a benzothiophenyl group, a dibenzothiophenyl group, or the like, an alkoxy group (e.g., preferably a carbon number). The carbon number is 丨~, and the most preferred one is carbon number 8, for example, methoxy, ethoxy, butoxy, etc.), aryloxy (preferably having a carbon number of 6 to 2 Å, preferably It is a carbon number of 6 to 16, particularly preferably a carbon number of 6 to 12, for example, a phenoxy group, a 2-naphthyloxy group or the like, and a mercapto group (preferably having a carbon number of 1 to 20, preferably a carbon number). Bu ^, particularly good for carbon number 1~12, for example: ethyl thiol, benzhydryl, methionyl, trimethylethyl, etc.), alkoxy groups (carbon number 2~2〇) Preferably, the carbon number is 2 to 16, and the carbon number is 2 to 12, for example, Methoxycarbonyl, ethoxycarbonyl. 11 2,009,327,095,101,520
基等)、芳氧基羰基(以碳數7〜20為佳,較佳者菩破叙7 特佳者為碳數7〜H),例如:苯氧基縣等)、醯氧基(以碳數 2〜2〇為佳,較佳者是碳數2〜16,特佳者為碳數2〜10,例如: 乙醯氧基、苯甲酿氧基等)、院硫基(以碳數㈣為佳較佳 者是碳數1〜16,特佳者為碳數丨〜12,例如:甲硫基、乙硫 基等)、芳硫基(以碳數6〜20為佳,較佳者是碳數6〜16,特 佳者為碳數6〜12,例如··苯硫基等)、取代或無取代之磺醯 基(以碳數1〜20為佳,較佳者是碳數卜16,特佳者為碳數 1〜12,例如:甲磺醯基、甲苯磺醯基等)、取代或無取代之 亞續醯基(以碳數1〜20為佳,較佳者是碳數丨〜16,特佳者為 碳數1〜12,例如:甲亞磺醯基、苯亞磺醯基等)、羥基、巯 基、鹵素原子(例如:氟原子、氣原子、溴原子、碘原子)、 氰基、磺酸基、羧基、亞磺酸基、雜環基(以碳數〗〜^為佳, 較佳者是碳數1〜12 ’雜原子係例如含有氧原子、硫原子者, 具體而言可舉例如:呋喃基、噻吩基、苯并D等唑基、苯并 嗜*坐等)、石夕基(以碳數3〜40為佳,較佳者是碳數3〜3〇,特Base, etc.), aryloxycarbonyl (preferably having a carbon number of 7 to 20, preferably those having a carbon number of 7 to H), for example, a phenoxy group, etc., a decyloxy group Carbon number 2~2〇 is preferred, preferably carbon number 2~16, especially good carbon number 2~10, for example: ethoxylated, benzyloxy, etc.), hospital sulfur (carbon) The number (4) is preferably better, the carbon number is 1 to 16, the most preferred one is carbon number 丨~12, for example, methylthio group, ethylthio group, etc.), and the arylthio group is preferably 6 to 20 carbon atoms. The preferred ones are carbon numbers 6 to 16, particularly preferably carbon numbers 6 to 12, such as phenylthio groups, etc., substituted or unsubstituted sulfonyl groups (preferably having a carbon number of 1 to 20, preferably Carbon number 16, particularly preferred are carbon number 1 to 12, for example: methylsulfonyl, toluenesulfonyl, etc.), substituted or unsubstituted hydrazine (preferably having a carbon number of 1 to 20, preferably The carbon number is 1616, especially the carbon number is 1~12, for example, sulfinyl, phenylsulfinyl, etc., hydroxyl, sulfhydryl, halogen atom (for example: fluorine atom, gas atom, bromine Atom, iodine atom), cyano group, sulfonic acid group, carboxyl group, sulfinic acid group, heterocyclic group (in terms of carbon number) Preferably, it is preferably a carbon number of 1 to 12'. The hetero atom system contains, for example, an oxygen atom or a sulfur atom. Specific examples thereof include an oxazolyl group such as a furyl group, a thienyl group, and a benzo D group, and a benzene group. *Sit and wait), Shi Xiji (preferably carbon number 3~40, preferably carbon number 3~3〇, special
佳者為碳數3〜24 ’例如:三甲碎、三苯碎等)等。該等取代 基亦可再進一步取代。又’當取代基有二個以上時,有相 同或相異之取代基亦可。又,亦可於容許之情況下互相連 結形成環。 另外,當前述取代基更具有取代基時,取代基可舉例 如前述式(l)Ra〜Rd中顯示之相同基。以下,於式(1)〜(5)之各 基具有取代基時的取代基亦相同。 本發明中,前述取代基中,以烷基、烯基、芳基、二 12 200932709 苯并11 夫11 南芳基、二苯并硫苯基芳基為佳。 L]表示之取代或無取代之2價的連結基,可舉例如:取 代或無取代之核碳數6〜50的伸芳基(arylene)。具體而言,可 舉自下述芳基更去除1個氫原子後所得之2價的基為例。 Ο 10 15 苯基、1-萘基、2-萘基、1-蔥基、2-蔥基、9-蔥基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基、1-稠四苯基、2-稠四苯基、9-稠四苯基、1-祐基、2-祐基、4-祐基、2-聯苯 基、3-聯苯基、4-聯苯基、p-聯三苯-4-基、p-聯三苯-3-基、 p-聯二苯-2-基、m-聯二苯-4-基、m-聯二苯-3-基、in-聯三苯 -2-基、〇-甲苯基、m-甲苯基、p-甲苯基、p-t-丁苯基、p-(2-苯基丙基)苯基、3-甲基-2-萘基、4-曱基-1-萘基、4-甲基-1-蔥基、4’-甲基聯苯基、4”-t-丁基-P-聯三苯-4-基。 另外,前述連結基之取代基未包含取代或無取代之胺 基。 較佳之“可舉單鍵、或以下之連結基為例。 [化 11]The preferred ones are carbon numbers of 3 to 24 Å, for example, trimethyst, triphenyl ruthenium, and the like. These substituents can be further substituted. Further, when there are two or more substituents, the same or different substituents may be used. Further, it is also possible to form a loop by connecting to each other as permitted. Further, when the above substituent has a more substituent, the substituent may, for example, be the same group as shown in the above formula (1), Ra to Rd. Hereinafter, the substituents in the case where each of the groups (1) to (5) has a substituent are also the same. In the present invention, the above substituent is preferably an alkyl group, an alkenyl group, an aryl group, or a dibenzothiophenyl aryl group. The substituted or unsubstituted divalent linking group represented by L] may, for example, be substituted or unsubstituted arylene having a core carbon number of 6 to 50. Specifically, a divalent group obtained by removing one hydrogen atom from the following aryl group can be exemplified. Ο 10 15 phenyl, 1-naphthyl, 2-naphthyl, 1-onionyl, 2-onionyl, 9-onionyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl , 9-phenanthryl, 1-fused tetraphenyl, 2-fused tetraphenyl, 9-fused tetraphenyl, 1-youtyl, 2-youtyl, 4-youtyl, 2-biphenylyl, 3-biphenylyl , 4-biphenylyl, p-biphenyl-4-yl, p-biphenyl-3-yl, p-biphenyl-2-yl, m-biphenyl-4-yl, m-linked Diphenyl-3-yl, in-bitriphenyl-2-yl, fluorenyl-tolyl, m-tolyl, p-tolyl, pt-butylphenyl, p-(2-phenylpropyl)phenyl , 3-methyl-2-naphthyl, 4-mercapto-1-naphthyl, 4-methyl-1-onion, 4'-methylbiphenyl, 4"-t-butyl-P- Further, the substituent of the above-mentioned linking group does not contain a substituted or unsubstituted amino group. Preferably, the single bond or the following linking group is exemplified. [化11]
Ari&Ar2表示之取代或無取代之核碳數6〜50的芳基, 以取代或無取代之核碳數6〜20的芳基為佳,可舉例如:苯 13 200932709 基、1-秦基、2-秦基、1-威基、2-感基、9-蔥基、1-菲基、 2-菲基、3-菲基、4-菲基、9-菲基、1-稠四苯基、2-稠四苯 基、9-稠四苯基、1-芘基、2-芘基、4-芘基、2-聯苯基、3-聯苯基、4-聯苯基、p-聯二苯-4-基、p-聯二苯-3-基、p-聯 5 二苯-2-基、m-聯二苯-4-基、m-聯二苯-3-基、m-聯二苯-2-基、〇_甲苯基、m-曱苯基、p-曱苯基、p-t-丁苯基、p-(2-苯 基丙基)苯基、3-曱基-2-萘基、4-甲基-1-萘基、4-曱基-1-咸基、4’-曱基聯苯基、4”小丁基-p-聯二苯-4-基及下述顯不 之苯并菲基。 10 [化 12]Ari&Ar2 represents a substituted or unsubstituted aryl group having a core carbon number of 6 to 50, preferably a substituted or unsubstituted aryl group having a core carbon number of 6 to 20, and examples thereof include benzene 13 200932709 base, 1- Qin. Base, 2-methyl group, 1-carbyl group, 2-inductive group, 9-onion group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1- thick Tetraphenyl, 2-fused tetraphenyl, 9-fused tetraphenyl, 1-indenyl, 2-indenyl, 4-indenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl , p-biphenyl-4-yl, p-biphenyl-3-yl, p-biphenylene-2-yl, m-biphenyl-4-yl, m-biphenyl-3- , m-biphenyl-2-yl, fluorenyl-tolyl, m-fluorenylphenyl, p-fluorenylphenyl, pt-butylphenyl, p-(2-phenylpropyl)phenyl, 3- Mercapto-2-naphthyl, 4-methyl-1-naphthyl, 4-mercapto-1-ylidene, 4'-fluorenylbiphenyl, 4"-butyl-p-biphenyl-4 - a benzophenanthyl group which is not shown below. 10 [Chemical 12]
(式中,Rb及q與前述式⑴相同。) 另外,前述核碳數6〜50之芳基的取代基未包含取代或 無取代之胺基。 15 八^及八巧,以取代或無取代之核碳數10~20的縮合芳香 族環基為佳。 取代或無取代之核碳數10〜20的縮合芳香族環基之具 體例,可舉例如:1-萘基、2-萘基、1-蔥基、2-蔥基、9-蔥 基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基、及4-甲基 20 -1-蔥基。(In the formula, Rb and q are the same as those in the above formula (1).) Further, the substituent of the aryl group having 6 to 50 carbon atoms does not contain a substituted or unsubstituted amino group. 15 八和和八巧, preferably substituted or unsubstituted condensed aromatic ring group with a nuclear carbon number of 10-20. Specific examples of the substituted or unsubstituted fused aromatic ring group having 10 to 20 nucleus carbon atoms include, for example, 1-naphthyl group, 2-naphthyl group, 1-onion group, 2-onion group, and 9-onion group. 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, and 4-methyl 20-1-onion.
Ar3表示之取代或無取代之核碳數10〜50的縮合芳香族 14 200932709 環基’可舉例如:1-萘基、2-萘基、1-蔥基、2-蒽基、9-蔥 基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基、1-稠四苯 基、2-稠四笨基、9_稠四苯基、丨_芘基、2_芘基、4_芘基、 3-曱基-2-萘基、4-曱基_ι_萘基、及4-甲基-1-蔥基。以取代 5或無取代之萘基為佳。又,亦以無取代之核碳數10〜20的縮 合芳香族環基為佳。 另外’前述核碳數1〇〜5〇之縮合芳香族環基的取代基未 包含取代或無取代之胺基。 © 以下顯示本發明之縮合芳香環衍生物的具體例。 ίο [化 13] ❿ 15 200932709Ar3 represents a substituted or unsubstituted condensed aromatic group having a nuclear carbon number of 10 to 50. 200932709 The ring group may, for example, be 1-naphthyl, 2-naphthyl, 1-onionyl, 2-indenyl, 9-onion Base, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-fused tetraphenyl, 2-fused tetraphenyl, 9-fused tetraphenyl, hydrazine Indenyl, 2-hydrazino, 4-hydrazino, 3-mercapto-2-naphthyl, 4-indolyl-ι-naphthyl, and 4-methyl-1-onion. It is preferred to substitute a 5- or unsubstituted naphthyl group. Further, it is also preferred to use an unsubstituted aromatic ring group having a nuclear carbon number of 10 to 20 as an unsubstituted. Further, the substituent of the condensed aromatic ring group having the above-mentioned core carbon number of 1 〇 to 5 Å does not contain a substituted or unsubstituted amine group. © Specific examples of the condensed aromatic ring derivative of the present invention are shown below. Οο [Chem. 13] ❿ 15 200932709
16 20093270916 200932709
17 20093270917 200932709
18 20093270918 200932709
19 20093270919 200932709
20 20093270920 200932709
21 20093270921 200932709
本發明之縮合芳香環衍生物可藉由例如:合成溴化苯 并菲衍生物,再與蒽衍生物之硼酸化合物反應調製。 5 另外,前述蔥及苯并菲係下述化合物。 22 10 200932709 5 [化 14]The condensed aromatic ring derivative of the present invention can be prepared, for example, by synthesizing a brominated benzophenanthrene derivative and reacting with a boronic acid compound of an anthracene derivative. 5 Further, the onion and the benzophenanthrene are the following compounds. 22 10 200932709 5 [Chem. 14]
蔥shallot
本發明之縮合芳香環衍生物可作為有機E L元件用材 料’特别可作為其發光材料使用。 10 本發明之有機EL元件具有陽極與陰極、及被挾持於陽 與陰極之間且含發光層之i層以上的有機薄膜層,有機薄 膜層之至少一層含有前述本發明之化合物。 本發明之有機EL元件的代表性構造,可舉例如: (1)陽極/發光層/陰極 15 (2)陽極/電洞注入層/發光層/陰極 (3) 陽極/發光層/電子注入層/陰極 (4) 陽極/電洞注入層/發光層/電子注入層/陰極 (5) 陽極/有機半導體層/發光層/陰極 (6) 陽極/有機半導體層/電子障壁層/發光層/陰極 20 (7)陽極/有機半導體層/發光層/附著改善層/陰極 (8) 陽極/電洞注入層/電洞輸送層/發光層/電子注入層/ 陰極 (9) 陽極/絶緣層/發光層/絶緣層/陰極 (10) 陽極/無機半導體層/絶緣層/發光層/絶緣層/陰極 23 200932709 (11) 陽極/有機半導體層/絶緣層/發光層/絶緣層/陰極 緣 (12) %極/絶緣層/電洞注入層/電洞輸送 層/陰極 /電子 (13) 陽極/絶緣層/電洞注入層/電洞輸送層/發光層 注入層/陰極 等並未限定於該等。該等中,通常以使用⑻之構 造為佳。 © 於第1圖顯不⑻之構造。該有機EL元件係由陽極1〇與 陰極2〇、及被挾持於其間之電洞注入層30、電洞輸送層32、 ⑺發光層34、電子注入層36構成。電洞注入層、電洞輪送 層32發光層34、及電子注入層36,相當於複數之有機薄 膜層。該等有機薄膜層3〇、32、34、36之至少一層,含有 本發明之化合物。 ❹ 本發明之有機EL元件中,本發明之化合物雖亦可用於 15前述之任-有機薄膜層,但以於發光層中使用為佳。本發 明之化合物,於各有機薄膜層中,可單獨使用,亦可與其 他化合物混合使用。本發明之元件中,以發光層含有作為 主體(host)材料之本發明化合物,且含有螢光性摻雜物及磷 光性摻雜物之至少1種為佳。 »0 . ^ 本發明中,以發光層實質上由本發明之化合物、及前 述摻雜物構成為佳。 另外,本發明之化合物於有機薄膜層中所佔之含有 量’以30〜100莫耳%為佳。 以下,說明有機EL元件之各構件。 24 200932709 有機EL元件通常係於基板上製作,基板會支撐有機EL 元件。以使用平滑之基板為佳。透過基板操取光時,基板 具透光性,且以波長400〜700nm之可見光領域之光透射率 為50%以上者為佳。 5 此種透光性基板,以使用例如,玻璃板、合成樹脂板 等為佳。玻璃板可舉例如:鈉鈣玻璃、鋇·锶含有玻璃、鉛 玻璃、鋁矽酸玻璃、硼矽酸玻璃、鋇硼矽酸玻璃、石英等 板。又,合成樹脂板可舉例如:聚碳酸酯樹脂、丙烯基樹 月曰、聚對苯二甲酸乙二酯樹脂、聚硫醚樹脂、聚硬樹脂等 10 板。 陽極將電洞注入電洞注入層、電洞輸送層或發光層, 可有效地具有4.5eV以上之工作函數。陽極材料之具體例, 可舉例如·乳化銦錫(ITO)、氧化銦與氧化鋅之混合物、IT〇 與氧化鈽之混合物、ΙΖΟ與氧化鈽之混合物、氧化銦與氧化 15鈽之混合物、氧化鋅與氧化鋁之混合物(ΑΖΟ)、氧化錫 (NESA)、金、銀、鉑、銅等。 陽極係由該等電極物質可以蒸鍍法或濺鍍法等形成。 當發光層之發光是自陽極操取時,以相對於陽極發光 的透射率大於10%為佳。又,陽極的薄片電阻係以數百Ω/π 20以下為佳。陽極的膜厚雖亦與材料相關,但通常為 10nm〜Ιμηι,以 1〇〜200nm為佳。 發光層具有以下機能。 (1)注入機能:施加電場時,可藉由陽極或電洞注入層 注入電洞,且可藉由陰極或電子注入層注入電子之機能。 25 200932709 (i〇輸送機能:以電場之力使已注 移動的機能。 入之電荷(電子及電洞) (iii)發光機能:使電子與電洞再結合, 的機能。 而與發光相連結 形成發光層的方法,可使用例如··蒸鍍法 法' LB(LangmUir-Bl〇dgett)法等習知的方法。發 分子堆舰為佳。此處之分子堆積膜係由氣態 形成發光層的方法, 分子堆積膜為佳。 物沉積所形成的膜、 '旋轉塗布 習知的方法。發光層特別以 態之材料化合 或由溶液狀態或液態之材料化合物固 體化所形成的膜,通常此種分子堆積膜,與藉由⑺法所形 ⑺成的膜(分子累積膜),可藉由凝集構造、高階構造的不同、 或以此等不同為由之機能上的差異來區分。 又,將樹脂等接著劑與材料化合物溶於溶劑而形成漆 液後,藉由旋轉塗布法等將溶液薄膜化亦可形成發光層。 如前述,發光層以含有將本發明之化合物作為主體讨 15料為佳。發光層除了本發明之化合物以外,可更含有下述 主體材料。 可使用於發光層之主體材料的具體例,可舉下述⑴〜(ix) 表示之化合物為例。 下述式(i)表示之非對稱葱。 20 [化 15]The condensed aromatic ring derivative of the present invention can be used as a material for an organic EL element, particularly as a light-emitting material. The organic EL device of the present invention comprises an anode and a cathode, and an organic thin film layer sandwiched between the anode and the cathode and having an i layer or more of the light-emitting layer, and at least one layer of the organic thin film layer contains the compound of the present invention. A representative configuration of the organic EL device of the present invention may, for example, be: (1) anode/light-emitting layer/cathode 15 (2) anode/hole injection layer/light-emitting layer/cathode (3) anode/light-emitting layer/electron injection layer / Cathode (4) Anode / Hole Injection Layer / Light Emitting Layer / Electron Injection Layer / Cathode (5) Anode / Organic Semiconductor Layer / Light Emitting Layer / Cathode (6) Anode / Organic Semiconductor Layer / Electronic Barrier Layer / Light Emitting Layer / Cathode 20 (7) Anode/organic semiconductor layer/light-emitting layer/adhesion improving layer/cathode (8) anode/hole injection layer/hole transport layer/light-emitting layer/electron injection layer/cathode (9) anode/insulation/lighting Layer/Insulation Layer/Cathode (10) Anode/Inorganic Semiconductor Layer/Insulation Layer/Light Emitting Layer/Insulation Layer/Cathode 23 200932709 (11) Anode/Organic Semiconductor Layer/Insulation Layer/Light Emitting Layer/Insulation Layer/Cathode Edge (12) % pole/insulation layer/hole injection layer/hole transport layer/cathode/electron (13) anode/insulation layer/hole injection layer/hole transport layer/light-emitting layer injection layer/cathode, etc. are not limited to these . Among these, it is generally preferred to use the configuration of (8). © Figure 1 shows the structure of (8). This organic EL element is composed of an anode 1 and a cathode 2, a hole injection layer 30 held therebetween, a hole transport layer 32, (7) a light-emitting layer 34, and an electron injection layer 36. The hole injection layer, the hole transfer layer 32, and the electron injection layer 36 correspond to a plurality of organic thin film layers. At least one of the organic thin film layers 3, 32, 34, 36 contains the compound of the present invention. In the organic EL device of the present invention, the compound of the present invention may be used in the above-mentioned any-organic thin film layer, but it is preferably used in the light-emitting layer. The compound of the present invention may be used singly or in combination with other compounds in each of the organic film layers. In the device of the present invention, it is preferred that the light-emitting layer contains the compound of the present invention as a host material, and at least one of a fluorescent dopant and a phosphorescent dopant is preferable. In the present invention, it is preferred that the light-emitting layer is substantially composed of the compound of the present invention and the above-mentioned dopant. Further, the content of the compound of the present invention in the organic film layer is preferably from 30 to 100 mol%. Hereinafter, each member of the organic EL element will be described. 24 200932709 Organic EL elements are usually fabricated on a substrate that supports the organic EL elements. It is preferable to use a smooth substrate. When the light is transmitted through the substrate, the substrate is translucent, and the light transmittance in the visible light region having a wavelength of 400 to 700 nm is preferably 50% or more. For the light-transmitting substrate, for example, a glass plate, a synthetic resin plate or the like is preferably used. The glass plate may, for example, be soda lime glass, barium, strontium containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz or the like. Further, the synthetic resin sheet may, for example, be a polycarbonate resin, an acrylic resin, a polyethylene terephthalate resin, a polythioether resin or a polyhard resin. The anode injects the hole into the hole injection layer, the hole transport layer or the light-emitting layer, and can effectively have a work function of 4.5 eV or more. Specific examples of the anode material include, for example, emulsified indium tin (ITO), a mixture of indium oxide and zinc oxide, a mixture of IT〇 and cerium oxide, a mixture of cerium and cerium oxide, a mixture of indium oxide and oxidized 15 Å, and oxidation. A mixture of zinc and alumina (ΑΖΟ), tin oxide (NESA), gold, silver, platinum, copper, and the like. The anode is formed of such an electrode material by a vapor deposition method, a sputtering method, or the like. When the luminescence of the luminescent layer is operated from the anode, the transmittance with respect to the luminescence of the anode is preferably greater than 10%. Further, the sheet resistance of the anode is preferably several hundred Ω / π 20 or less. Although the film thickness of the anode is also related to the material, it is usually 10 nm to Ιμηι, preferably 1 Å to 200 nm. The luminescent layer has the following functions. (1) Injection function: When an electric field is applied, a hole can be injected through an anode or a hole injection layer, and electrons can be injected by a cathode or an electron injection layer. 25 200932709 (I〇 Conveyor function: the function of moving the electric field with the force of the electric field. The charge (electron and hole)) (iii) The function of illuminating: the function of recombining electrons with holes, and connecting with the illuminating As a method of forming the light-emitting layer, a conventional method such as a vapor deposition method 'LB (LangmUir-Bl〇dgett) method can be used. It is preferable to use a molecular bomber. The molecular deposition film here forms a light-emitting layer from a gaseous state. The method, the molecular deposition film is preferred. The film formed by the deposition of the material, the method of the spin coating is known. The luminescent layer is formed by a combination of a material of a state or a solidification of a compound in a solution state or a liquid material, usually The molecular deposition film and the film (molecular accumulation film) formed by the method (7) by the method (7) can be distinguished by the difference in function between the agglutination structure, the high-order structure, or the like. After the binder and the material compound are dissolved in a solvent to form a lacquer liquid, the solution can be formed into a light-emitting layer by a spin coating method or the like. As described above, the light-emitting layer contains the compound of the present invention as a main body. In addition to the compound of the present invention, the light-emitting layer may further contain the following host material. Specific examples of the host material for the light-emitting layer may be exemplified by the following compounds (1) to (ix). The asymmetric onion represented by formula (i). 20 [Chem. 15]
26 200932709 (式中,ArQG1係取代或無取代之核碳數10〜50(以l〇〜3〇 為佳,較佳者是10〜20)的縮合芳香族基。ArQQ2係取代或無 取代之核碳數6〜50(以6〜20為佳,較佳者是6~14)的芳香族 基。 5 e 10 15 ❹ 20 χ_〜χ〇〇3自 6〜50(以6〜20為佳,較佳者是6〜14)之芳香族基、取代或無 取代之核原子數5〜50(以5〜20為佳)的芳香族雜環基、取代 或無取代之碳數1〜50(以1〜20為佳,較佳者是1〜12,特佳者 為1〜8)的烷基、取代或無取代之碳數1〜50(以1〜20為佳,較 佳者是1〜12,特佳者為1〜8)的烷氧基、取代或無取代之礙 數6〜50(以6〜20為佳,較佳者是6〜14)的芳烷基、取代或無 取代之核原子數5〜50(以5〜20為佳)的芳氧基、取代或無取 代之核原子數5〜50(以5〜20為佳)的芳硫基、取代或無取代 之碳數1〜50(以1〜20為佳,較佳者是1〜12,特佳者為1〜8)的 院氧基幾基、叛基、齒素原子、氰基、靖基 '經基。a、b 及c各係〇〜4之整數。η係1〜3之整數。又,當n為2以上時,[] 内可相同或相異。) 另外,當前述ArG<)1等之基具有取代基時,取代基可舉 與前述式(1)之Ra〜Rd顯示之例相同的基為例。又,亦可為取 代或無取代之胺基。本說明書中,於後述各式顯示之基具 有取代基時亦相同。 下述式(ii)表示之非對稱單蔥衍生物。 [化 16] 27 20093270926 200932709 (In the formula, ArQG1 is a substituted or unsubstituted condensed aromatic group having a nuclear carbon number of 10 to 50 (preferably 10 to 3, preferably 10 to 20). ArQQ2 is substituted or unsubstituted. An aromatic group having a core carbon number of 6 to 50 (preferably 6 to 20, preferably 6 to 14). 5 e 10 15 ❹ 20 χ _ χ〇〇 3 from 6 to 50 (6 to 20 is preferred) , preferably 6 to 14) of an aromatic group, a substituted or unsubstituted core having 5 to 50 (preferably 5 to 20) aromatic heterocyclic group, substituted or unsubstituted carbon number 1 to 50 Preferably, the alkyl group, substituted or unsubstituted carbon number is from 1 to 20, preferably from 1 to 20, preferably from 1 to 12, preferably from 1 to 20 (preferably from 1 to 20, preferably from 1 to 12, particularly preferably 1 to 8) alkoxy, substituted or unsubstituted, 6 to 50 (preferably 6 to 20, preferably 6 to 14) aralkyl, substituted or An unsubstituted aryloxy group having 5 to 50 (preferably 5 to 20) aryloxy group, substituted or unsubstituted aryl group having 5 to 50 (preferably 5 to 20), substituted or unsubstituted The number of carbon atoms is 1 to 50 (1 to 20 is preferred, preferably 1 to 12, and the preferred one is 1 to 8). , cyano, Jingji's radicals, a, b, and c are integers of 〇~4. η is an integer of 1 to 3. Further, when n is 2 or more, [] may be the same or different.) When the substituent of the above ArG<1>1 or the like has a substituent, the substituent may be exemplified by the same examples as those shown by Ra to Rd in the above formula (1). Further, it may be a substituted or unsubstituted amino group. In the present specification, the same applies to the substituents shown in the following formulas. An asymmetric onion derivative represented by the following formula (ii). [化16] 27 200932709
(式中,ArQG3及Ar_係各自獨立之取代或無取代的核破 數6〜50(以6〜20為佳,較佳者是6〜14)之芳香族環基,瓜及11 各係1〜4之整數。但是,於m=n=l且Ar’與ArQG4之苯環結合 5 位置為左右對稱型時,ArGG3與ArGG4不同,於m或η為2〜4之 整數時,m與η係相異之整數。 R001〜RG1G係各自獨立之氫原子、取代或無取代之核碳 數6〜50(以6〜20為佳,較佳者是6〜14)的芳香族環基、取代 或無取代之核原子數5〜50(以5〜20為佳)的芳香族雜環基、 10 取代或無取代之碳數1〜50(以1〜20為佳,較佳者是1〜12,特 佳者為1〜8)的烷基、取代或無取代之環烷基、取代或無取 代之碳數1〜50(以1〜20為佳,較佳者是1〜12,特佳者為1〜8) 的烧氧基、取代或無取代之碳數6〜50(以6〜20為佳,較佳者 是6~14)的芳烷基、取代或無取代之核原子數5〜5〇(以5~2〇 15為佳)的芳氧基、取代或無取代之核原子數5〜50(以5〜20為 佳)的方硫基、取代或無取代之碳數1〜5〇(以1〜2〇為佳,較 佳者疋1〜12,特佳者為1~8)的烧乳基幾基、取代或無取代 之矽基、羧基、li素原子、氰基、硝基、羥基。) 下述式(iii)表示之非對稱芘衍生物。 20 [化 17] 200932709(In the formula, ArQG3 and Ar_ are each independently substituted or unsubstituted, and the number of cores is 6 to 50 (preferably 6 to 20, preferably 6 to 14), aromatic ring groups, melons and 11 systems. An integer of 1 to 4. However, when m=n=l and the position where Ar' is bonded to the benzene ring of ArQG4, the position is different, and ArGG3 is different from ArGG4. When m or η is an integer of 2 to 4, m and An integer of η is different from each other. R001 to RG1G are independent hydrogen atoms, substituted or unsubstituted aryl groups having 6 to 50 (preferably 6 to 20, preferably 6 to 14) aromatic groups. A substituted or unsubstituted core atom number of 5 to 50 (preferably 5 to 20) of an aromatic heterocyclic group, 10 substituted or unsubstituted carbon number of 1 to 50 (preferably 1 to 20, preferably 1) ~12, particularly preferably 1 to 8) alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted carbon number 1 to 50 (preferably 1 to 20, preferably 1 to 12, Particularly preferred are an alkoxy group, substituted or unsubstituted nucleus having 1 to 8) alkoxy groups, substituted or unsubstituted carbon numbers of 6 to 50 (preferably 6 to 20, preferably 6 to 14). The number of atoms having 5 to 5 Å (preferably 5 to 2 〇 15), the number of aryloxy groups, substituted or unsubstituted, and 5~ 50 (5 to 20 is preferred) of a thiol group, a substituted or unsubstituted carbon number of 1 to 5 Å (preferably 1 to 2 Å, preferably 疋 1 to 12, and particularly preferably 1 to 8) An alkyl group, a substituted or unsubstituted fluorenyl group, a carboxyl group, a li atom, a cyano group, a nitro group, a hydroxyl group.) An asymmetric anthracene derivative represented by the following formula (iii). 20 [Chem. 17] 200932709
((L〇〇2 卜 Ar〇0' [式中,ArGG5及ArG()0各係取代或無取代之核碳數 6〜50(以6〜20為佳,較佳者是6〜14)的芳香族基。 LQQ1及IT2各係取代或無取代之伸苯基、取代或無取代 5 之伸萘基(naphthalenylene)、取代或無取代之伸莱基 (fluorenylene)、或取代或無取代之二苯并亞矽烷基 (dibenzosilolylene)。 m係0〜2之整數,η係1~4之整數,s係0〜2之整數,t係〇〜4 之整數。 10 又,L_或Αι^5係結合於芘之編號1〜5之位置的任一 者,LGG2或ArQG6係結合於芘之編號6〜10之位置的任一者。 但,當n+t為偶數時,Ar005、Ar006、L_、L002係滿足下述(1) 或(2)之條件。 ⑴ArGG5MrGQ6及/或IT VL°G2(此處之#係表示相異構造 15 之基團。) (2)當 Ar°°5=Ar_ 且 L_:=L°〇2 時 (2-l)m>s及/或n#t、或 (2-2)m=s 且 n=t 時, (2·2-1)當IT1及LQQ2、或芘各結合於ArGG5及Ar006上相異 20之結合位置時,或者當(2-2-2) L_及LGG2、或芘於ArG()5及 29 200932709((L〇〇2 卜Ar〇0' [wherein, ArGG5 and ArG()0 are substituted or unsubstituted, and the number of carbon atoms is 6 to 50 (preferably 6 to 20, preferably 6 to 14) Aromatic groups. LQQ1 and IT2 are substituted or unsubstituted phenyl, substituted or unsubstituted 5 naphthalenylene, substituted or unsubstituted fluorenylene, or substituted or unsubstituted Dibenzosilolylene. m is an integer from 0 to 2, η is an integer from 1 to 4, s is an integer from 0 to 2, and t is an integer from 〇 to 4. 10 Further, L_ or Αι^ 5 is a combination of any of the positions 1 to 5 of the 芘, and LGG2 or ArQG6 is bonded to any of the positions 6 to 10. However, when n+t is an even number, Ar005, Ar006, L_ and L002 satisfy the following conditions (1) or (2): (1) ArGG5MrGQ6 and/or IT VL°G2 (where # is a group representing a distinct structure 15) (2) When Ar°°5= Ar_ and L_:=L°〇2 (2-l)m>s and/or n#t, or (2-2)m=s and n=t, (2·2-1) when IT1 and LQQ2, or 芘 each binds to a binding position of different 20 on ArGG5 and Ar006, or when (2-2-2) L_ and LGG2, or ArARG()5 and 29 200932709
j, ^UUo I I Γ 相同的結合位置結合時,L。01及IT2、或ArQG5及Ar_ 於疙之取代位置不會在編號1及6之位置、或編號2及7位 置。] 下述式(IV)表示之非對稱蒽衍生物。 5 [化 18] 018j, ^UUo I I 时 When the same binding position is combined, L. 01 and IT2, or ArQG5 and Ar_ are not substituted at positions 1 and 6, or numbers 2 and 7. An asymmetric anthracene derivative represented by the following formula (IV). 5 [18] 018
017 002 R016 Ar008 (iv) ArUU7 R 015 020017 002 R016 Ar008 (iv) ArUU7 R 015 020
(式中,Α_及aQG2係各自獨立之取代或無取代之核場 數10〜20的縮合芳香族環基。 取 10(wherein, Α_ and aQG2 are independently substituted or unsubstituted condensed aromatic ring groups having a number of nuclear fields of 10 to 20.
Ar_及Ar_係各自獨立之氫原子、或者取代或無取代 之核碳數6〜50(以6〜20為佳,較佳者是6〜14)的芳香族環某 R011〜RG2G係各自獨立之氫原子、或者取代或無取代之 核碳數6〜50(以6〜20為佳,較佳者是6〜14)的芳香族環美 取代或無取代之核原子數5〜50(以5~20為佳)的芳$ 基、取代或無取代之碳數1〜50(以1〜20為佳# I β 1〜12,特佳者為1〜8)的烧基、取代或無取代之環貌基 代或無取代之碳數1〜50(以1〜20為佳,較佳者是 a ’特佳 者為1〜8)的烷氧基、取代或無取代之碳數6〜5〇(以6〜2〇為 佳,較佳者是6〜14)的芳烧基、取代或無取代之核原子數 30 15 200932709 5〜50(以5〜20為佳)的芳氧基、取代或無取代之核原子數 5〜50(以5〜20為佳)的芳硫基、取代或無取代之碳數以 1〜20為佳,較佳者是1〜12,純者為卜8)祕氧基叛基、 取代或無取代之矽基、綾基、^素原子、氰基、硝基或羥 基。Ar°°7、Ar°°7、R°19及R°2°可各形成為複數,亦可以鄰接 之兩者形成飽和或不飽和的環狀構造。 但是,式(iv)中,中心之蔥的編號9位置及1〇位置處,Ar_ and Ar_ are each independently a hydrogen atom, or a substituted or unsubstituted nucleocarbon having a carbon number of 6 to 50 (preferably 6 to 20, preferably 6 to 14), and each of the R011 to RG2G systems An independent hydrogen atom, or a substituted or unsubstituted core carbon number of 6 to 50 (preferably 6 to 20, preferably 6 to 14), an aromatic ring-substituted or unsubstituted core atom number of 5 to 50 ( a 5 to 20-based, substituted or unsubstituted carbon number of 1 to 50 (1 to 20 is preferably # I β 1 to 12, particularly preferably 1 to 8) of the alkyl group, substitution or Unsubstituted ring-shaped or unsubstituted carbon number 1 to 50 (preferably 1 to 20, preferably a 'excellent is 1 to 8) alkoxy group, substituted or unsubstituted carbon number 6~5〇 (preferably 6~2〇, preferably 6~14) aryl group, substituted or unsubstituted core atom number 30 15 200932709 5~50 (5~20 is better) The aryl, substituted or unsubstituted aryl group having 5 to 50 (preferably 5 to 20) arylthio group, substituted or unsubstituted carbon number is preferably 1 to 20, preferably 1 to 12, pure. It is a hydroxy group, a substituted or unsubstituted sulfhydryl group, a fluorenyl group, a halogen atom, a cyano group, a nitro group. A hydroxyl group. Ar°°7, Ar°°7, R°19, and R°2° may each be formed in a plural number, or both of them may form a saturated or unsaturated annular structure. However, in the formula (iv), the center of the onion is numbered 9 and 1〇,
並無相對於該蒽上所示之χ_γ軸而相對稱之對稱型之基團 相結合的情況。) 10 下述式(V)表示之蔥衍生物。 [化 19]There is no case where a symmetrical group of symmetry is combined with respect to the χγ axis shown on the 蒽. 10) An onion derivative represented by the following formula (V). [Chem. 19]
(式中,RG21〜R_係各自獨立之氫原子、烷基、環烷基、 取代亦可之芳基、烷氧基、芳氧基、烷胺基、烯基、芳胺 15 基或取代亦可之雜環基。a及b各表示1〜5之整數,當該等為 2以上時,R021群或R022群於各群中可相同或相異,又,尺奶 群或RG22群亦可結合形成環,R023與rg24、rG2^r〇26、R〇27 與RG28、rq29與rG3Q亦可互相結合形成環。 L_表示單鍵、_〇-、-S-、-N(R)-(R係烷基或取代亦可 2〇 之芳基)、伸烷基或伸芳基。) 31 200932709 下述式(vi)表示之蒽衍生物。 [化 20](wherein, RG21 to R_ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, a substituted aryl group, an alkoxy group, an aryloxy group, an alkylamino group, an alkenyl group, an arylamine group or a substituent. A heterocyclic group may also be used. Each of a and b represents an integer of 1 to 5, and when the ratio is 2 or more, the R021 group or the R022 group may be the same or different in each group, and the milk group or the RG22 group is also Can form a ring, R023 and rg24, rG2^r〇26, R〇27 and RG28, rq29 and rG3Q can also combine to form a ring. L_ represents a single bond, _〇-, -S-, -N(R) - (R is an alkyl group or a substituted aryl group), an alkyl group or an aryl group.) 31 200932709 An anthracene derivative represented by the following formula (vi). [Chem. 20]
(式中,R031〜R_各自獨立表示氫原子、烷基、環烷基、 5 芳基、烷氧基、芳氧基、烷胺基、芳胺基、或取代亦可之 雜環基。c、d、e及f各表示1〜5之整數,當該等為2以上時, R031群、R032群、R036群或R037群於各群中可相同亦可相異, 又,R031群、RQ32群、RQ33群或R037群亦可結合形成環,R033 與RQ34、^°39與11_亦可互相結合形成環。 10 LQQ4表示單鍵、-0-、-S-、-N(R)-(R係烷基或取代亦可(wherein R031 to R_ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a 5-aryl group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamine group, or a heterocyclic group which may be substituted. c, d, e, and f each represent an integer from 1 to 5, and when the ratio is 2 or more, the R031 group, the R032 group, the R036 group, or the R037 group may be the same or different in each group, and the R031 group, The RQ32 group, the RQ33 group or the R037 group may also combine to form a ring, and R033 and RQ34, ^39 and 11_ may also be combined to form a ring. 10 LQQ4 represents a single bond, -0-, -S-, -N(R) -(R-alkyl or substituted
之芳基)、伸烷基或伸芳基。) 下述式(vii)表示之螺第(spirofluorene)衍生物。 [化 21]An aryl group, an alkyl group or an aryl group. A spirofluorene derivative represented by the following formula (vii). [Chem. 21]
A007 A008 (vii) 15 (式中,aQQ5〜aQQ8係各自獨立且取代或無取代之聯苯 32 200932709 基、或者取代或無取代之萘基。) 下述式(viii)表示之含有縮合環化合物。 [化 22] A〇11A007 A008 (vii) 15 (wherein aQQ5~aQQ8 are each independently and substituted or unsubstituted biphenyl 32 200932709 group, or a substituted or unsubstituted naphthyl group.) The following formula (viii) represents a condensed ring compound . [化 22] A〇11
5 (式中,AQU〜AG13係各自獨立之取代或無取代之核碳數 6〜50(以6〜20為佳,較佳者是6〜14)的伸芳基。AG14〜AG16係 各自獨立之氫原子、或取代或無取代之核碳數6〜50(以6〜20 為佳,較佳者是6〜14)的芳基。R041〜RG43係各自獨立表示氫 原子、碳數1〜6之烷基、碳數3〜6之環烷基、碳數1〜6之烷氧 10基、碳數5〜18之芳氧基、碳數7〜18之芳烷基氧基、碳數5〜16 之芳胺基、梢基、氰基、碳數1〜6之醋基、或鹵素原子, A〇ii〜中之至少1者係具有3環以上之縮合芳香族環的5 (wherein AQU~AG13 are independently substituted or unsubstituted, and the number of carbon atoms is 6 to 50 (preferably 6 to 20, preferably 6 to 14). The AG14 to AG16 are independent. The hydrogen atom or the substituted or unsubstituted aryl group having a core carbon number of 6 to 50 (preferably 6 to 20, preferably 6 to 14). R041 to RG43 each independently represent a hydrogen atom and a carbon number of 1 to 1. 6 alkyl group, carbon number 3 to 6 cycloalkyl group, carbon number 1 to 6 alkoxy 10 group, carbon number 5 to 18 aryloxy group, carbon number 7 to 18 aralkyloxy group, carbon number 5 to 16 of an arylamine group, a terminal group, a cyano group, a carboxylic acid group having 1 to 6 carbon atoms, or a halogen atom, and at least one of A〇ii~ has a condensed aromatic ring having 3 or more rings.
(式中,R051及R052表示氫原子、取代或無取代之烧基、 33 200932709 取代或無取代之芳烷基、取代或無取代之芳基、取代或無 取代之雜環基、取代胺基、氰基或南素原子。結合於相異 之苐基的R05丨群、R052群可相同或相異,結合於相同之第基 的rq51及R°52可相同或相異。 5 尺咖及1^54表示氫原子、取代或無取代之烷基、取代或 無取代之芳烷基、取代或無取代之芳基、或者取代或無取 代之雜環基,結合於相異之苐基的R〇53群、R〇54群可相同或 相異,結合於相同之苐基的R〇5^R〇54可相同或相異。(wherein R051 and R052 represent a hydrogen atom, a substituted or unsubstituted alkyl group, 33 200932709 substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted amine group , cyano or a sulphide atom. The R05 丨 group and the R052 group which are bound to the different sulfhydryl groups may be the same or different, and rq51 and R°52 which are combined with the same base group may be the same or different. 1^54 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, which is bonded to a different fluorenyl group. The R〇53 group and the R〇54 group may be the same or different, and R〇5^R〇54 bound to the same thiol group may be the same or different.
Ar011及Ar012表示合計有3個以上笨環之取代或無取代 ❹ 10之縮合多環芳香族基、或者以合計有3個以上苯環與雜環之 取代或無取代之碳而結合至苐基的縮合多環雜環基。Aron 及ArQ12可相同或相異。η表示1〜1〇之整數。) 本發明之有機EL元件中,以發光層含有以本發明化合 — 物作為主體’且含有碌光性掺雜物、及螢光性摻雜物之至 15少一者為佳。又,於含有本發明化合物之發光層,亦可積 層含有該等摻雜物之發光層。Ar011 and Ar012 represent a condensed polycyclic aromatic group having three or more acyclic rings substituted or unsubstituted fluorene, or a substituted or unsubstituted carbon having three or more benzene rings and a hetero ring in total, and bonded to a fluorenyl group. Condensed polycyclic heterocyclic group. Aron and ArQ12 can be the same or different. η represents an integer of 1 to 1 〇. In the organic EL device of the present invention, it is preferable that the light-emitting layer contains the compound of the present invention as a main body and contains at least one of a light-emitting dopant and a fluorescent dopant. Further, in the light-emitting layer containing the compound of the present invention, a light-emitting layer containing the dopants may be laminated.
Q 礙光性摻雜物係可由三重態激子(triplet excit〇n)發光 之化合物。由三重態激子發光時,並未特別限定,但以含 有選自於由Ir、Ru、Pd、pt、Os、及Re所構成之群之至少 20 種金屬的金屬錯合物為佳。又,以叶琳(porphyrin)金屬錯 合物或正金屬化(ortho metalation)金屬錯合物為佳。填光性 化合物可單獨使用,亦可併用2種以上。 4琳金屬錯合物以卟啉鉑錯合物為佳。 作為形成正金屬化金屬錯合物之配位子有許多種類, 34 200932709 較佳的配位子,可舉例如:具有苯基^定骨架、聯β比咬骨 架或啡啉(phenamhroline)骨架之化合物、或2苯基吡啶衍生 物、7,8_苯并啥嘛衍生物、2_(2_喧吩基)n比唆衍生物、2仆 萘基)魏衍生物、2·苯基㈣魅物等。該等之配位子亦 5可視需要具有取代基。特別是,以導入有氣化物、三氣甲 基者作為藍色系掺雜物為佳。此外,亦可具有作為補助配 位子之乙醯丙酮、苦酸等上述配位子以外之配位子。 ❹Q Light-blocking dopants are compounds that can be illuminated by triplet excitons. The light emitted by the triplet exciton is not particularly limited, but a metal complex containing at least 20 metals selected from the group consisting of Ir, Ru, Pd, pt, Os, and Re is preferable. Further, a porphyrin metal complex or an ortho metalation metal complex is preferred. The light-filling compound may be used singly or in combination of two or more. 4 Lin metal complex is preferably porphyrin platinum complex. There are many types of ligands for forming a positive metallated metal complex, and 34 200932709 preferred ligands include, for example, a phenyl group, a beta-bite skeleton or a phenamhroline skeleton. a compound, or a 2 phenylpyridine derivative, a 7,8-benzopyrene derivative, a 2-(2-aminophenyl)n-p-anthracene derivative, a 2-propenyl-based derivative, a 2-phenyl group (four) charm Things and so on. These ligands may also have substituents as desired. In particular, it is preferred to use a vapor-based or tris-methyl group as a blue-based dopant. Further, it may have a ligand other than the above-described ligand such as acetamidine or picric acid as a supplementary ligand. ❹
此種金屬錯合物之具體例,可舉例如:三(2_苯級咬) 錶、三(2-苯基吼咬)舒、三(2_苯基吼。定)銳、雙(2苯純淀) 1〇鉑、三(2-苯基錢)锇、三(2_苯基㈣)鍊、八乙基翻口卜淋、 八苯基鉑斗啉、八乙基鈀外啉、八苯基鈀外啉等,但並未 限定於該等,可依所需之發光色、元件性能、使用之主體 化合物選擇適合的錯合物。 填光性掺雜物之發光層的含有量並未特別制限,可視 15目的適當地選擇,可舉〇 ]〜?〇質量%為例,以Μ。質量%為 佳。當磷光性化合物之含有量小於〇1質量%時,有發光微 弱且無法充分發揮其含有效果的疑慮,當大於川質量% 時,則有所謂之濃度淬滅現象顯著,且造成元件性能下降 之疑慮。 螢光性摻雜物以依所需發光顏色選自於由下述組合的 化合物為佳:胺系化合物、芳香族化合物、三(8-羥基喹啉) 鋁(tris(8-quinolin〇late)aiuminium)錯合物等螯合錯合物、香 豆靈衍生物、四苯基丁二烯衍生物、雙芪類衍生物、噚二 唑衍生物等。較佳者是苯乙烯胺化合物、苯乙烯二胺化合 35 200932709 物、芳胺化合物、芳二胺化合物。又,亦以非胺系化合物 之縮合多環芳香族化合物為佳。該等螢光性摻雜物可單獨 或組合複數使用。 螢光性摻雜物在發光層中的含量並未特別限制,可視 5目的適當地選擇,例如,相對於發光層全體之質量,係 0·01〜100質量%,以0.1〜30質量%為佳。 苯乙烯胺化合物及苯乙烯二胺化合物,以下述式(A)表 示者為佳。 [化 24] 〇Specific examples of such a metal complex include, for example, a tris(2_benzene-based bite) table, a tris(2-phenylindole), a tris(2-phenylene group), a sharp, and a double (2). Benzene pure lake) 1 〇 platinum, tris(2-phenyl hydrazine) ruthenium, tris(2-phenylene) chain, octaethyl thiophene, octaphenylplatinum, octaethyl palladium, Although octaphenyl palladium or the like is not limited thereto, a suitable complex can be selected depending on the desired luminescent color, element performance, and the host compound to be used. The content of the light-emitting layer of the light-filling dopant is not particularly limited, and may be appropriately selected depending on the purpose of the first embodiment, and may be exemplified by 〇. The mass % is better. When the content of the phosphorescent compound is less than 〇1% by mass, there is a concern that the light emission is weak and the effect of the content is not sufficiently exhibited. When the amount is more than the mass% of the product, there is a so-called concentration quenching phenomenon and the element performance is degraded. doubt. The fluorescent dopant is preferably selected from the group consisting of the following compounds in a desired luminescent color: an amine compound, an aromatic compound, and tris (8-quinolinium) aluminum (tris (8-quinolin) Chelating complexes such as aiuminium complex compounds, coumarin derivatives, tetraphenylbutadiene derivatives, biguanide derivatives, oxadiazole derivatives, and the like. Preferred are styrylamine compounds, styrene diamine compounds 35 200932709, arylamine compounds, and aryldiamine compounds. Further, a condensed polycyclic aromatic compound of a non-amine compound is also preferred. These fluorescent dopants may be used singly or in combination. The content of the fluorescent dopant in the light-emitting layer is not particularly limited, and may be appropriately selected depending on the purpose of the light-emitting layer, for example, from 0. 01 to 100% by mass, and from 0.1 to 30% by mass based on the total mass of the light-emitting layer. good. The styrylamine compound and the styrene diamine compound are preferably represented by the following formula (A). [化 24] 〇
/ Ar102 Ar1014-N \ Ar103 10 (A) (式中’ Ar1G1係p價基,係與苯基、萘基、聯苯基、三 聯苯基(terphenyl)、芪基(stilbenyl)、二苯乙烯芳基 ' (distyrylaryl)對應的p價基;Ari〇2及Ari〇3各係碳數6〜2〇(以 6〜14為佳)之芳香族烴基(ar〇niatic hydrocarbon group),且 15 Ar1Q1、Ar102及Ar1。3亦可被取代。Ari。丨〜Ari〇3之任一者是經 ❹ 本乙烯基取代的。更佳者是,Ar1G2或Ar103之至少一者是經 苯乙烯基取代的。卩係丨〜4之整數,以1〜2之整數為佳。) 此處,碳數6〜20(以6〜14為佳)的芳香族烴基,可舉例 如:苯基、萘基、苯甲醯亞胺酸(anthranii)基、菲基、三聯 20 苯基等。 芳胺化合物及芳二胺化合物,以下述式(B)表示者為 佳0 36 200932709 [化 25j/ Ar102 Ar1014-N \ Ar103 10 (A) (wherein Ar1G1 is a p-valent group with a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a stilbenyl group, a stilbene group a p-valent group corresponding to distyrylaryl; Ari〇2 and Ari〇3 each having an aromatic hydrocarbon group of 6 to 2 Å (preferably 6 to 14), and 15 Ar1Q1 Ar102 and Ar1.3 may also be substituted. Any of Ari.丨~Ari〇3 is substituted with a quinone vinyl group. More preferably, at least one of Ar1G2 or Ar103 is substituted with a styryl group. The integer of 卩 4 4 4 is preferably an integer of 1 to 2. Here, the aromatic hydrocarbon group having 6 to 20 carbon atoms (preferably 6 to 14) may, for example, be a phenyl group, a naphthyl group or a benzene group. Anthraniic acid, phenanthryl, triple 20 phenyl, and the like. The arylamine compound and the aryldiamine compound are preferably represented by the following formula (B). 0 36 200932709 [Chemical 25j
Ar1114-NAr1114-N
5 ❹ 10 ❹ 15 (式中’ Ar111係q價之取代或無取代之核碳數5〜4〇(以 6〜20為佳,較佳者是6〜14)的芳香族基,Ar112、Ar113各係取 代或無取代之核碳數5〜40(以6〜20為佳’較佳者是6〜14)的 芳基。q係1〜4之整數,以1〜2之整數為佳。) 此處’核碳數5〜40之芳基,可舉例如:苯基、萘基、 本甲醯亞胺酸基、菲基、祐基、襄基(C〇r〇nenyl)、聯苯基、 三聯苯基、β比略基、咬喃基、嘆吩基、苯并嗟吩基、π等二 唑基、二苯基苯甲醯亞胺酸基、吲哚基、咔唑基、吡啶基、 苯并啥琳基、螢蒽基(fluoranthenyl)、苊并螢蒽基 (acenaphthofluoranthenyl)、芪基、茈基、蒯基(chrySenyl)、 涟基(picenyl)、聯三苯基、祐基(rubicenyl)、苯并蒽基、苯 胺苯甲酸(phenylanthranil)基、二蒽基(bisanthracenyl)等。以 萘基、苯甲醯亞胺酸基、蒯基、芘基為佳。 Ar111以前述q價之基為佳,又,當Ar111為2價時,以下 述式(C)、(D)表示之基為佳,且以式(D)表示之基較佳。 [化 26]5 ❹ 10 ❹ 15 (In the formula, Ar111 is a substituted or unsubstituted nucleus having 5 to 4 fluorene (preferably 6 to 20, preferably 6 to 14) aromatic groups, Ar112, Ar113 Each of the substituted or unsubstituted nucleophilic groups having 5 to 40 (preferably 6 to 20 is preferably '6 to 14). The q is an integer of 1 to 4, preferably an integer of 1 to 2. Here, the aryl group having a nuclear number of 5 to 40 may, for example, be a phenyl group, a naphthyl group, a methionine group, a phenanthryl group, a ketone group, a fluorenyl group (C〇r〇nenyl), or a biphenyl group. , terphenyl, β-l-butyl, tert-butyl, succinyl, benzoquinole, π, etc. oxazolyl, diphenyl benzhydrazinyl, fluorenyl, carbazolyl, pyridine Benzo, benzophenanyl, fluoranthenyl, acenaphthofluoranthenyl, sulfhydryl, sulfhydryl, chrySenyl, picenyl, triphenyl, rubicenyl ), benzofluorenyl, phenylanthranil, bisanthracenyl, and the like. The naphthyl group, the benzamidine acid group, the fluorenyl group and the fluorenyl group are preferred. Ar111 is preferably a group having the above q-valent group. When Ar111 is divalent, the group represented by the following formulas (C) and (D) is preferred, and the group represented by the formula (D) is preferred. [Chem. 26]
(C) (D) 37 200932709 (式(c)中,〜3之整數。) 另外’取代前述芳基之較佳取代基,可舉例如:碳數 1〜6之炫基(乙基、甲基、丨_丙基、n_丙基、s 丁基、t·丁基' 戊基、己基、環戊基、環己基等)、碳數1〜6之烧氧基(乙氧 5基、甲氧基、丨丙氧基、η-丙氧基、s-丁氧基、t-丁氧基、 戊氧基、己氧基、環戊氧基、環己氧基等)、核碳數5〜4〇(以 6〜20為佳’較佳者是6〜Η)之芳基、經核碳數5〜40之芳基取 代的胺基、具有核碳數5〜4G之芳基_旨基、具有碳數卜6 之烷基的酯基、氰基、硝基、自素原子等。 ❹ 1〇 發光層亦可視需要,含有電洞輸送材料、電子輸送材 料、或高分子接合劑。 發光層之膜厚以5〜50nm為佳,較佳者是7〜5〇nm,最佳 者為10〜5Gnm。當小於5nm時,有不易形成發光層,且色度 調整困難之疑慮,當大於5〇咖時,則有驅動電壓上升之疑 15 慮。 電洞注入層及電洞輸送層係幫助朝發光層之電洞注入 而輸送至發光領域之層,電洞移動性大,離子化能量通常 〇 為5挪以下之小值。此種電淘注入層及電洞輸送層的材 Μ更低電㈣度下,將電洞輸送至發光層的材料為 又’電洞的移動性係以例如在施加1〇4〜脚/咖之電場 時’ 秒以上為佳。 電洞注入層及電洞輸送層之材料並未特別限定,可任 ί由習知在㈣導材料中作為電洞的電荷輪送材料所慣用 者、或有機EL元件之電洞注入層及電洞輸送層所使用之眾 38 200932709 所周知之物令選擇使用。 於電洞注入層及電洞輸送層中,可使用例如,下述式 表示之芳香族胺衍生物。 [化 27](C) (D) 37 200932709 (in the formula (c), an integer of ~3.) Further, a preferred substituent for the substitution of the above aryl group may, for example, be a condensed group having a carbon number of 1 to 6 (ethyl, A). Base, 丨-propyl, n-propyl, s-butyl, t-butyl 'pentyl, hexyl, cyclopentyl, cyclohexyl, etc.), alkoxy groups having 1 to 6 carbon atoms (ethoxy 5 groups, Methoxy, decyloxy, η-propoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclopentyloxy, cyclohexyloxy, etc.), nuclear carbon number 5 to 4 〇 (6 to 20 is preferred 'preferably 6 to Η) aryl group, amine group substituted with aryl group having 5 to 40 carbon atoms, and aryl group having 5 to 4 G carbon number _ An ester group having an alkyl group having a carbon number of 6, a cyano group, a nitro group, a self-priming atom or the like. ❹ 1〇 The luminescent layer may also contain a hole transporting material, an electron transporting material, or a polymeric binder, as needed. The film thickness of the light-emitting layer is preferably 5 to 50 nm, more preferably 7 to 5 nm, and most preferably 10 to 5 Gnm. When it is less than 5 nm, there is a fear that it is difficult to form a light-emitting layer, and chromaticity adjustment is difficult. When it is more than 5 Å, there is a concern that the driving voltage rises. The hole injection layer and the hole transport layer help to inject holes into the light-emitting layer and transport them to the layer of the light-emitting region. The hole mobility is large, and the ionization energy is usually a small value of 5 or less. The material of the electric injection layer and the hole transport layer is lower (at the fourth degree), and the material for transporting the hole to the light-emitting layer is 'the mobility of the hole, for example, when applying 1〇4~foot/coffee The electric field is better than seconds. The material of the hole injection layer and the hole transport layer is not particularly limited, and may be any one of conventionally used as a charge transfer material for a hole in a (four) conductive material, or a hole injection layer of an organic EL element and electricity. The use of the hole transport layer 38 200932709 is known to use. For the hole injection layer and the hole transport layer, for example, an aromatic amine derivative represented by the following formula can be used. [化27]
Ar211〜Ar213、Ar221〜Ar223及Ar2Q3〜At·2。8各係取代或無取 代之核碳數6〜50(以6〜20為佳’較佳者是6〜14)的芳香族煙 基、或取代或無取代之核原子數5〜50(以5〜20為佳)的芳香 族雜環基。a〜c及p〜r各係〇〜3之整數。Ar203與Ar204、Ar205 10與Ar2G6、Ar207與Ar2G8亦可各互相連結形成飽和或不飽和之 環。 取代或無取代之核碳數6〜50的芳香族烴基之例,可舉 例如:苯基、1-萘基、2-萘基、1·蒽基、2-蔥基、9-蒽基、 1-菲基、2·菲基、3-菲基、4-菲基、9-菲基、1-祠四笨基、 15 2_稠四苯基、9-稠四苯基、1-芘基、2-芘基、4-芘基、2_聯 苯基、3-聯苯基、4-聯苯基、p_聯三苯_4_基、p_聯三笨 基、p-聯三苯-2-基、m-聯三苯-4-基、m-聯三苯-3-展、 土 Hi- 聯三苯-2-基、〇-甲苯基、m-曱苯基、p-曱苯基、p_t_丁笨基、 p-(2-苯基丙基)苯基、3-曱基-2-萘基、4-甲基-1-萘基、4_甲 20基-1-蔥基、4’-甲基聯苯基、4”-t-丁基-p-聯三苯-4-基。 39 200932709 取代或無取代之核原子數5〜50的芳香族雜環基之例, 可舉例如:K絲、2·轉基、H略基、*嗪基、2_吼 咬基、3音定基、4_吼啶基、丨矧哚基、2,哚基、3十朵 基、4_。引。朵基、5·,π朵基、6·,β朵基、7_π引嗓基、丨·異叫卜朵 5基、2_異吲哚基、3-異吲哚基、4-異吲哚基、5_異吲哚基、 6-異吲D木基、7-異吲哚基、2-"夫喃基、3-吱喃基、2-苯并呋 喃基、3-苯并呋喃基、4-苯并呋喃基、5_苯并呋喃基、6_苯 并呋喃基、7-苯并吱喃基、1-異苯并呋喃基、3_異苯并呋喃 基、4-異苯并呋喃基、5-異苯并呋喃基、6_異苯并呋喃基、 © 10 7-異苯并呋喃基、喹啉基、3·喹啉基、4_喹啉基、5喹啉基、 6-啥啉基、7-喹啉基、8-喹啉基' 1_異喹啉基、3-異喹啉基、 4-異喹啉基、5-異喹啉基、6-異喹啉基、7-異喹啉基、8-異 喹啉基、2-喳喏啉基(quinoxalinyi)、5-喳喏啉基、6-喳喏啉 - 基、1-咔唑基、2-咔唑基、3-咔唑基、4-咔唑基、9-咔唑基、 15丨_啡啶基、2_啡啶基、3-啡啶基、4-啡啶基、6-啡啶基、7-啡啶基、8-啡啶基、9-啡啶基、1〇_啡啶基、1_吖啶基、2-吖啶基、3-吖啶基、4-吖啶基、9_吖啶基、ι,7·啡啉 〇 (phenantliroline)-2-基、1,7-啡啉-3_基、L7-啡啉-4-基、1,7-啡琳-5-基、1,7-啡琳-6-基、1,7_啡琳_8基、1,7-#琳-9-基、 20 1,7-_琳-10-基、1,8-啡琳-2-基、1,8_徘嚇_3_基、1,8-啡琳-4-基、1,8-啡啉-5-基、1,8-啡啉-6-基、1,8-啡啉-7-基、1,8-啡 琳-9·基、1,8-°非琳-10-基、1,9-啡琳_2_基、1,9-啡琳-3-基、 1,9-啡啉-4-基、1,9-啡啉-5-基、丨,…啡啉各基、ι,9·啡啉-7-基、1,9-# 琳-8-基、1,9-啡琳·ι〇_基、1,1〇__琳-2-基、1,10- 4〇 200932709 啡琳-3-基、U〇_D非琳-4_基、n非琳_5_基、2,9_啡啉小 基、2,9-啡琳_3_基、2,9-啡琳-4-基、2,9_,非琳_5_基、2,9^非 啉_6-基、2,9-啡啉-7-基、2,9-哄啉_8_基、2,9__琳_1〇_基、 μ-啡琳-i-基、2,8_啡琳_3_基、2,8_啡琳_4_基、2,8_啡^_ 5基、2,8-啡琳-6-基、2,8-啡琳-7-基、2,8_啡琳_9-基、2,8•哪 啉_10-基、2,7-啡啉-1-基、2,7-啡啉_3_基、2,7_啡啉_4基、 2,7-哪啉-5-基、2,7-啡琳-6-基、2,7-«非琳-8-基、2,7-啡琳_9 基、2,7-啡琳-ίο-基、ι_啡畊基(phenazinyl)、2_。非畊基、1 啡嘍啡基(phenothiazinyl)、2-啡嘍啡基、3_啡嘍讲基、釦啡 1〇嘍畊基、10-啡嘍讲基、丨_吩呤嗪基、2_吩噚嗪基、3_吩气 嗪基、4-吩噚嗪基、10_吩谔嗪基、2·噚唑啉基、4_哼唑啉 基、5-噚唑啉基、2_噚二唑啉基、5_谔二唑啉基、3_呋咕基 (3-furazanyl)、2-噻吩基、3·噻吩基、2_甲基吡咯小基、厶 甲基吡咯-3-基、2-甲基吡咯-4-基、2-甲基吡咯_5-基、3_甲 15基0比嘻基、3-曱基0比嘻-2-基、3-甲基比洛·4_基、3-甲基 吡咯-5-基、2-t-丁基吡咯-4-基、3-(2-苯基丙基)吡咯•基、 2_甲基弓丨0朶基、4-甲基-1-»引u朶基、2-甲基_3-π弓丨〇朶基、4 甲基-3-»弓丨哚基、2-t-丁基-1-0弓丨嵘基、4小丁基朵基、2 t 丁基-3-"引嵘基、4-t-丁基-3-"引哚基。 20 此外,於電洞注入層及電洞輸送層中,可使用下述式 表示之化合物。 [化 28] 41 200932709Ar211~Ar213, Ar221~Ar223 and Ar2Q3~At·2. 8 substituted or unsubstituted nucleocarbon number 6~50 (6~20 is preferred 'better is 6~14) aromatic smoky group, Or a substituted or unsubstituted aromatic heterocyclic group having a nuclear atom number of 5 to 50 (preferably 5 to 20). a ~ c and p ~ r each system 〇 ~ 3 integer. Ar203 and Ar204, Ar205 10 and Ar2G6, Ar207 and Ar2G8 may each be bonded to each other to form a saturated or unsaturated ring. Examples of the substituted or unsubstituted aromatic hydrocarbon group having a core carbon number of 6 to 50 include, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a fluorenyl group, a 2-onion group, and a 9-fluorenyl group. 1-phenanthryl, phenanthrenyl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-indolyl, 15- 2 fused tetraphenyl, 9-fused tetraphenyl, 1-anthracene , 2-indenyl, 4-indenyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, p-biphenyl-4-yl, p-linked triphenyl, p-linked Triphenyl-2-yl, m-biphenyl-4-yl, m-biphenyl-3-extension, soil Hi-biphenyl-2-yl, fluorenyl-tolyl, m-fluorenylphenyl, p - fluorenylphenyl, p_t_buttytyl, p-(2-phenylpropyl)phenyl, 3-mercapto-2-naphthyl, 4-methyl-1-naphthyl, 4-methyl-2-yl- 1-Onion, 4'-methylbiphenyl, 4"-t-butyl-p-biphenyl-4-yl. 39 200932709 Substituted or unsubstituted aromatic heterocycle having 5 to 50 core atoms Examples of the group include, for example, K-filament, 2·transalkyl, H-radyl, oxazinyl, 2-anthracene, 3-tone base, 4-acridinyl, fluorenyl, 2, fluorenyl, 3 ten bases, 4 _. 引.,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Indenyl, 4-isoindenyl, 5-isodecyl, 6-isoindole D-based, 7-isodecyl, 2-"-folly, 3-indolyl, 2-benzene And furyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzopyranyl, 1-isobenzofuranyl, 3_ Isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, ©10 7-isobenzofuranyl, quinolyl, 3·quinolinyl, 4-quinolinyl, 5-quinolinyl, 6-carbolinyl, 7-quinolyl, 8-quinolinyl '1-isoquinolyl, 3-isoquinolinyl, 4-isoquinolinyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolinyl, quinoxalinyi, 5-carbolyl, 6-carboline - group, 1-carbazolyl, 2-oxazolyl, 3-oxazolyl, 4-oxazolyl, 9-oxazolyl, 15-indolyl, 2-cylinyl, 3-cyridinyl , 4-cyridinyl, 6-cyridinyl, 7-cyridinyl, 8-cyridinyl, 9-cyridinyl, 1-indolyl, 1-cyridinyl, 2-acridinyl , 3-acridinyl, 4-acridinyl, 9-acridinyl, iota, phenantliroline-2-yl, 1,7-morpholine -3_yl, L7-morpholin-4-yl, 1,7-morphin-5-yl, 1,7-morphine-6-yl, 1,7-morphine-8, 1,7- #琳-9-基,20 1,7-_琳-10-基,1,8-morphine-2-yl, 1,8_徘吓_3_ base, 1,8-morphine-4- 1,1,8-morpholin-5-yl, 1,8-morpholin-6-yl, 1,8-morpholin-7-yl, 1,8-morphine-9-yl, 1,8- °非琳-10-yl, 1,9-morphine-2-yl, 1,9-morphin-3-yl, 1,9-morpholin-4-yl, 1,9-morpholin-5- Base, hydrazine, ... phenanthroline, i, 9, phenanthroline-7-yl, 1,9-# lin-8-yl, 1,9-carnation, ι〇_yl, 1,1〇__ Lin-2-yl, 1,10- 4〇200932709 morphine-3-yl, U〇_D non-lin-4_yl, n-non-lin_5_yl, 2,9-phenanthroline, 2, 9-morphine _3_yl, 2,9-morphin-4-yl, 2,9_, non-lin _5-yl, 2,9^ phenanthroline-6-yl, 2,9-morpholin-7 -yl, 2,9-carboline _8_yl, 2,9__lin_1〇_yl, μ-morphine-i-yl, 2,8-morphine_3_yl, 2,8-morphine琳_4_基,2,8_啡^_ 5 base, 2,8-morphine-6-yl, 2,8-morphine-7-yl, 2,8-morphine_9-yl, 2 ,8•Nanolin_10-yl, 2,7-morpholin-1-yl, 2,7-morpholine-3-yl, 2,7-phenanthroline-4-yl, 2,7-morpholin-5 -yl, 2,7-morphine-6-yl, 2,7-«non-lin-8-yl, 2,7-morphine _9 base, 2,7-morphine- ίο-based, ι_ phenazinyl, 2_. Non-cultivated, phenothiazinyl, 2-morphinyl, 3-cyanoquinone, cyanobacteria, 10-cyanoquinone, 丨-phenoxazine, 2 _ phenoxazine, 3_phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl, 2·oxazoline, 4-oxazolyl, 5-oxazolinyl, 2_ Oxadiazolinyl, 5-oxadiazolyl, 3-furazanyl, 2-thienyl, 3-thiophenyl, 2-methylpyrrole, 厶methylpyrrole-3- Base, 2-methylpyrrol-4-yl, 2-methylpyrrole-5-yl, 3-methyl-15-yl- 0-indenyl, 3-indolyl 0-indol-2-yl, 3-methylpiro · 4_yl, 3-methylpyrrole-5-yl, 2-t-butylpyrrol-4-yl, 3-(2-phenylpropyl)pyrrolidinyl, 2-methylpyridinium 0 , 4-methyl-1-» 引 乌, 2-methyl_3-π 丨〇 丨〇, 4-methyl-3-» 丨哚 、, 2-t-butyl-1-0 Cyclodecyl, 4 butylbutyl, 2 t butyl-3-" fluorenyl, 4-t-butyl-3-" Further, in the hole injection layer and the hole transport layer, a compound represented by the following formula can be used. [化 28] 41 200932709
(式中Ar〜Ar34各係取代或無取代之核碳數6〜5〇(以 6〜20為佳,憾者是6,的芳錢烴基、或者取代或無取 代之核原子數5〜50(以5〜20為佳)的芳香族雜環基。[係連結 5基、單鍵、或者取代或無取代之核碳數6〜50(以6〜20為佳, 較佳者;1:6〜14)的料族烴基、或者取代或無取代之核原子 數5〜50(以5〜20為佳)的芳香族雜環基。义係〇〜5之整數。A,2 與Ar233亦可互相連結形成飽和或不飽和之環。) 此處取代或無取代之核碳數6〜5〇的芳香族烴基、及取 10代或無取代之核原子數5~50的芳香族雜環基之具體例,可 舉與前述芳香族胺衍生物相同者為例。 此外,電洞注入層及電洞輸送層之材料的具體例,可 舉例如:***衍生物、噚二唑衍生物、咪唑衍生物、聚芳 烷(polyarylalkane)衍生物、吡唑啉衍生物、吡唑琳酮衍生 15 物、苯二胺(Phenylenediamine)衍生物、芳胺(arylamine)衍 生物、胺基取代之查耳酮(chalcone)衍生物、$唾衍生物、 笨乙烯基蒽(styrylanthracene)衍生物、第酮衍生物、腙衍生 物、1,2-二苯乙烯衍生物(芪衍生物)、矽氮類衍生物、苯胺 系共聚物、及導電性高分子募聚物(特別是噻吩募聚物)等。 電洞注入層及電洞輸送層之材料可使用前述者,但以 20 200932709 5 使用°卜琳化合物、芳香族第三級胺化合物及苯乙稀胺化合 物’特別以使用芳香族第三級胺化合物為佳。 又’分子内具有2個縮合芳香族環之化合物以使用下 J為1例如4·4'雙(Ν-(1·萘基)-N-苯胺)聯苯(以下略稱 為NPD)、或三笨胺單元連結至3個歸狀(starburst)型之 4,4,,4,,-三(叫甲基苯基)善苯胺)三苯胺(以下略稱為 MTDATA)等。 ❹ 此外,亦可使用下述式表示之含氮雜環衍生物。 [化 29] 10 严N,1 N 丫^ΓΝ、κ2。2 R2vV^ 一“2。3 ❹ (式中,R °〜R2。%表示取代或無取代之燒基、取代或 無取代之芳基、取代或無取代之芳烷基、取代或無取代之 雜環基的任一者。R201 與R2G2、R203與R2。4、R205與r2G6、r201 與R2Q6、R2G2與R2。3、或R2M與R2G5亦可形成縮合環。) 15 又,亦可使用下述式之化合物。 [化 30] 43 200932709 5 10(In the formula, Ar~Ar34 is substituted or unsubstituted, and the number of carbon atoms is 6 to 5 Å (preferably 6 to 20, and 6 is an aromatic hydrocarbon group, or a substituted or unsubstituted nuclear atom number 5 to 50). An aromatic heterocyclic group (preferably 5 to 20). [Coupling a 5-group, a single bond, or a substituted or unsubstituted nucleus carbon number of 6 to 50 (preferably 6 to 20, preferably; 1: 6 to 14) a hydrocarbon group of a hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group having a nuclear atom number of 5 to 50 (preferably 5 to 20). An integer of 〇 ~ 5 is also used. A, 2 and Ar 233 are also They may be bonded to each other to form a saturated or unsaturated ring.) The substituted or unsubstituted aromatic hydrocarbon group having 6 to 5 carbon atoms and the aromatic heterocyclic ring having 5 or 50 carbon atoms in 10 or unsubstituted form. Specific examples of the base are exemplified as the above-mentioned aromatic amine derivative. Specific examples of the material of the hole injection layer and the hole transport layer include a triazole derivative and an oxadiazole derivative. , imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolinone derivatives 15, phenylenediamine derivatives, arylamine derivatives Amine-substituted chalcone derivative, saliva derivative, styrylanthracene derivative, ketone derivative, anthracene derivative, stilbene derivative (anthracene derivative) ), a nitrogen-based derivative, an aniline-based copolymer, and a conductive polymer-polymer (especially a thiophene-polymerized polymer), etc. The material of the hole injection layer and the hole transport layer can be used as described above, but 20 200932709 5 The use of °blin compounds, aromatic tertiary amine compounds and styrene amine compounds' is particularly preferred to use aromatic tertiary amine compounds. Also - compounds with two condensed aromatic rings in the molecule The lower J is 1 such as 4·4′ bis(indenyl-(1·naphthyl)-N-aniline)biphenyl (hereinafter abbreviated as NPD), or the tris-amine unit is linked to three starburst types. 4,4,,4,,-three (called methylphenyl) good aniline) triphenylamine (hereinafter abbreviated as MTDATA) and the like. Further, a nitrogen-containing heterocyclic derivative represented by the following formula may also be used. 10 严 N,1 N 丫^ΓΝ, κ2. 2 R2vV^ A "2.3 ❹ (wherein R ° R R 2 % represents a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl Any of aryl, substituted or unsubstituted heterocyclic groups of the group, substituted or unsubstituted, R201 and R2G2, R203 and R2. 4, R205 and r2G6, r201 and R2Q6, R2G2 and R2.3, or R2M A condensed ring may also be formed with R2G5.) 15 Further, a compound of the following formula may also be used. [Chem. 30] 43 200932709 5 10
(式中’ Rif係取代基,且以各自為氣基、 硫醯基、羰基、三氟甲基、齒素等拉電子美為佳 又,亦可使用P型Si、P型SiC等無機化合二為, 入層及電洞輸送層之材料。 ‘ | 峭基、 ㈣注入增及電洞輸送層係可藉真空基錢法、 布法、鑄製法、LB料眾所ma的方法,將前述化合^ 膜化而形H;眺人層及電崎送層之膜厚並未特別 制,但通常為5nm〜一。電洞注入層及電洞輸送層可由 述材料之一種或二種以上所形成之一層構成,亦可為將 相異化合物所形成之複數電洞注入層及電洞輸送層積 者。(In the formula, Rif is a substituent, and each of them is a gas-based, thiol-, carbonyl, trifluoromethyl, or dentate-like electron, and it is also possible to use inorganic compounds such as P-type Si and P-type SiC. The second is the material of the layer and the hole transport layer. ' | The base, the (4) injection and the hole transport layer can be borrowed by the vacuum method, the cloth method, the casting method, the LB material method, the aforementioned The film thickness of the ruthenium layer and the kisaki layer is not particularly prepared, but is usually 5 nm to 1. The hole injection layer and the hole transport layer may be one or more of the materials described. One layer structure may be formed, or a plurality of holes injection layers and hole transport layers formed by different compounds may be formed.
有機半導體層係幫助電洞或電子注入發光層之層,以 具有10_1GS/cm以上之導電率者為佳。此種有機半導體層^ 15材料,可使用含噻吩募聚物或含芳胺募聚物等導電性寡聚 物、含芳胺樹枝狀聚合物等導電性樹枝狀聚合物等。 電子注入層及電子輸送層係幫助電子注入發光層,並 輸送至發光領域之層,電子移動性大。又,附著改善層係 由特別是與陰極附著良好的材料所形成的電子注入層的二 種。The organic semiconductor layer is preferably used to facilitate the injection of holes or electrons into the layer of the light-emitting layer, and it is preferable to have a conductivity of 10_1 GS/cm or more. As the material of the organic semiconductor layer 15, a conductive oligomer such as a thiophene-based polymer or an aromatic amine-containing polymer or a conductive dendrimer such as an aromatic amine dendrimer can be used. The electron injecting layer and the electron transporting layer help electrons are injected into the light emitting layer and are transported to the layer of the light emitting region, and the electron mobility is large. Further, the adhesion improving layer is composed of two types of electron injecting layers formed of a material which adheres particularly to the cathode.
44 200932709 電子輸送層可適當地選擇5nm〜5μιη之膜厚,特別於膦 厚很厚時,為避免電壓上升,以選擇施加1〇4〜1〇6v/cm電場 時’電子移動度為10'W/Vs以上者為佳。 10 電子注入層及電子輸送層所使用之材料,以8_經基喧 琳或其衍生物之金屬錯合物、或4二嗤衍生物較佳。8_幾 基喹啉或其衍生物之金屬錯合物的具體例,可舉例如:含 有奥辛(oxine ; —般是8_羥基喹啉(8_hydr〇xyquin〇line或 8-quinolinol))之螯合物的金屬螯合物8_羥基喹琳酮 (chelated oxinoid)化合物,例如,三(8-羥基喹啉)鋁。 4二嗤衍生物,可舉以下式表示之電子傳達化合物為 例0 [化 31] ❹44 200932709 The electron transport layer can be appropriately selected from a film thickness of 5 nm to 5 μm, especially when the phosphine thickness is very thick, in order to avoid voltage rise, the electron mobility is 10' when an electric field of 1〇4~1〇6v/cm is applied. Those with W/Vs or higher are preferred. 10 The material used for the electron injecting layer and the electron transporting layer is preferably a metal complex of 8_ quinone or a derivative thereof, or a 4 fluorene derivative. Specific examples of the metal complex of 8_monoquinoline or a derivative thereof include, for example, oxine (oxine; 8_hydr〇xyquin〇line or 8-quinolinol). A metal chelate of a chelate is a chelated oxinoid compound, for example, tris(8-quinolinolato)aluminum. 4 diterpene derivative, which can be represented by the following formula: Example 0 [Chem. 31] ❹
Ar301Ar301
(•302 N—N N—N Ar303^ ^_Af304_^(•302 N—N N—N Ar303^ ^_Af304_^
Ar305 N—N N—N Ar306^ ^_Ar307_〇_Ar308^ Ar309 Ό 0 15 (式中,Ar301、Ar302、Ar303、Ar305、Ar306、及 Ar309各 表示取代或無取代之芳基。又,Ar3Q4、Ar3G7、Ar·各表示 取代或無取代之伸芳基。) 此處芳基可舉例如:苯基、聯苯基、苯甲醯亞胺酸 (anthranil)基、茈基、芘基等。又,伸芳基可舉例如:伸苯 基、伸萘基、聯伸二苯基(biphenylene)、伸苯甲醯亞胺酸 45 200932709 (anthranilene)基、伸茈基(perylenylene)、伸芘基(pyrenylene) 等。又,取代基可舉例如:碳數丨〜川之烷基、碳數丨〜⑺之 烷氧基或氰基等。該電子傳達化合物以薄膜形成性者為佳。 前述電子傳達性化合物之具體例,可舉下述者為例。 5 [化 32]Ar305 N—NN—N Ar306^^_Ar307_〇_Ar308^ Ar309 Ό 0 15 (wherein Ar301, Ar302, Ar303, Ar305, Ar306, and Ar309 each represent a substituted or unsubstituted aryl group. Further, Ar3Q4, Ar3G7 And Ar. each represents a substituted or unsubstituted extended aryl group.) The aryl group here may, for example, be a phenyl group, a biphenyl group, an anthranil group, an anthracenyl group or a fluorenyl group. Further, examples of the aryl group include a stretching phenyl group, a stretching naphthyl group, a biphenylene group, a benzamidine imidate 45 200932709 (anthranilene) group, a perylenylene group, and a perylene substrate. Pyrenylene) and so on. Further, the substituent may, for example, be an alkyl group having a carbon number of 川~chuan, an alkoxy group having a carbon number of (~(7) or a cyano group. The electron-transporting compound is preferably a film-forming one. Specific examples of the electron-transporting compound include the following. 5 [化32]
(Me表示甲基,t-Bu表示t丁基。) 又,電子注入層及電子輸送層所使用的材料,可使用 卞述式(E)〜(J)表示者。 〇 式(E)及式(F)表示之含氮雜環衍生物: [化 33] 46 200932709(Me represents a methyl group, and t-Bu represents a t-butyl group.) Further, materials used for the electron injecting layer and the electron transporting layer can be expressed by using the following formulae (E) to (J).含 A nitrogen-containing heterocyclic derivative represented by the formula (E) and the formula (F): [Chem. 33] 46 200932709
係取代或無取代之核碳數6〜60(以6〜20為佳,較佳者是6〜14) 的芳基、或者取代或無取代之核原子數3〜6〇(以3〜2〇為佳, 5較佳者是3~14)的雜芳基,Ar311’係取代或無取代之核原子數 6〜60(以6〜20為佳,較佳者是6〜14)的伸芳基、或者取代或 無取代之核碳數3〜60(以3〜20為佳、較佳者是3〜14)之雜伸 芳基、Ar312係氫原子、取代或無取代之核碳數6〜6〇(以6〜2〇 為佳,較佳者是6〜14)的芳基、取代或無取代之核原子數 10 3〜60(以3〜20為佳,較佳者是3〜14)的雜芳基、取代或無取 代之破數1〜20(以1〜12為佳,較佳者是1〜8)的烷基、或者取 代或無取代之碳數1〜20(以1〜12為佳’較佳者是1〜8)的烷氧 基。但是,Ar311及Ar312之任一者係取代或無取代之核碳數 10〜60(以1〇~30為佳,較佳者是1〇〜20)的縮合環基、或者取 15 代或無取代之核原子數3〜60(以3~20為佳,較佳者是3〜14) 單雜(monohetero)的縮合環基。 L311、L312及L313各係單鍵、取代或無取代之核碳數6〜6〇 的伸芳基、取代或無取代之核原子數3〜60的雜伸芳基、或 者取代或無取代伸苐基。 47 200932709 R及R311各係氫原子、取代或無取代之核碳數6〜60的芳 基、取代或無取代之核原子數3〜60的雜芳基、取代或無取 代之碳數1〜20(以1〜12為佳’較佳者是1〜8)的烷基、或者取 代或無取代之碳數卜20(以1〜12為佳,較佳者是丨〜8)的烷氧 5 基,η係0~5之整數,當η為2以上時,複數R可相同或相異, 又,亦可以鄰接之R基群結合形成碳環式脂肪族環或碳環式 芳香族環。) 式(G)所表示之含氮雜環衍生物: HAr-L314-Ar321-Ar322 (G) ® 10 (式中,HAr係亦可具有取代基之碳數3〜4〇(以3〜30為 佳,較佳者是3〜24)的含氮雜環,L314係單鍵、亦可具有取 代基之碳數6〜60(以6〜20為佳,較佳者是6〜14)的伸芳基、 亦可具有取代基之碳數3〜60(以3〜20為佳,較佳者是3〜14) 的雜伸芳基、或亦可具有取代基之伸第基,八^^係亦可具 15有取代基之碳數6〜60(以6〜20為佳,較佳者是6〜14)的2價芳 香族烴基,At·322係亦可具有取代基之碳數6〜6〇(以6〜2〇為 佳較佳者疋6〜14)的芳基、或亦可具有取代基之碳數 ^ 3〜60(以3〜20為佳,較佳者是3〜14)的雜芳基。) 气(Η}所表示之石夕環戊二稀(SilaCyel〇pentadiene)衍生 20 物: [化 34] 48 200932709 R303 r302 >304a substituted or unsubstituted aryl group having 6 to 60 carbon atoms (preferably 6 to 20, preferably 6 to 14) or a substituted or unsubstituted core having 3 to 6 Å (3 to 2) Preferably, 5 is preferably a heteroaryl group of 3 to 14), and the Ar311' is a substituted or unsubstituted core having a number of cores of 6 to 60 (preferably 6 to 20, preferably 6 to 14). An aryl group, or a substituted or unsubstituted nucleus having a carbon number of from 3 to 60 (preferably from 3 to 20, preferably from 3 to 14), an Ar312 hydrogen atom, a substituted or unsubstituted nucleus carbon number 6 to 6 〇 (preferably 6 to 2 Å, preferably 6 to 14) of an aryl group, a substituted or unsubstituted core atom number of 10 3 to 60 (preferably 3 to 20, preferably 3 ~14) a heteroaryl group, a substituted or unsubstituted alkyl group having 1 to 20 (preferably 1 to 12, preferably 1 to 8), or a substituted or unsubstituted carbon number of 1 to 20 ( The alkoxy group is preferably 1 to 12, preferably 1 to 8 carbon atoms. However, any of Ar311 and Ar312 is a substituted or unsubstituted fused ring group having a nuclear carbon number of 10 to 60 (preferably 1 to 30, preferably 1 to 20), or 15 generations or none. The number of nuclear atoms to be substituted is from 3 to 60 (preferably from 3 to 20, preferably from 3 to 14). A monohetero condensed cyclic group. L311, L312 and L313 are each a single bond, a substituted or unsubstituted aryl group having 6 to 6 fluorene, a substituted or unsubstituted heteroaryl group having a core number of 3 to 60, or a substituted or unsubstituted extension.苐基. 47 200932709 R and R311 are each a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 60 aryl groups, a substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms, a substituted or unsubstituted carbon number 1~ 20 (1 to 12 is preferred 'preferably 1 to 8) alkyl group, or substituted or unsubstituted carbon number 20 (preferably 1 to 12, preferably 丨 8) alkoxy 5 base, η is an integer of 0~5. When η is 2 or more, the plural Rs may be the same or different, or may be combined with adjacent R groups to form a carbocyclic aliphatic ring or a carbocyclic aromatic ring. . A nitrogen-containing heterocyclic derivative represented by the formula (G): HAr-L314-Ar321-Ar322 (G) ® 10 (wherein, the HAr group may have a substituent having a carbon number of 3 to 4 Å (3 to 30) Preferably, it is preferably 3 to 24) of a nitrogen-containing heterocyclic ring, and the L314 is a single bond, and may have a substituent having a carbon number of 6 to 60 (preferably 6 to 20, preferably 6 to 14). An extended aryl group having a carbon number of from 3 to 60 (preferably from 3 to 20, preferably from 3 to 14), or a stretching group which may have a substituent, may also have a substituent. The system may have a substituted carbon number of 6 to 60 (preferably 6 to 20, preferably 6 to 14) of a divalent aromatic hydrocarbon group, and the At. 322 system may have a carbon number of the substituent. 6 to 6 〇 (6 to 2 〇 is preferred, 疋 6 to 14) of the aryl group, or may have a substituent carbon number of 3 to 60 (preferably 3 to 20, preferably 3 ~14) Heteroaryl.) SilaCyel〇pentadiene represented by gas (Η) 20 species: [Chem. 34] 48 200932709 R303 r302 >304
χ301 γ301 (Η) (式中’ X及Υ各係碳_數1〜6之飽和或不飽和之煙 基、烧氧基、烯氧基、块氧基(alkynyloxy)、經基、取代或 無取代之芳基、取代或無取代之雜環、或者又與丫結合而形 ❹Χ301 γ301 (Η) (in the formula, X and Υ each series of carbon _ number 1 to 6 of saturated or unsaturated ketone, alkoxy, alkenyloxy, alkynyloxy, thiol, substituted or none Substituted aryl, substituted or unsubstituted heterocyclic ring, or combined with hydrazine
5成飽和或不飽和之環的構造。R3G1〜R3G4各係氫、函素原子、 院基、烧氧基、芳氧基、全氟烧基、全敗炫氧基、胺基、 炫基、方Ik基、烧氧幾基、芳氧幾基(aryloxycarbonyl)、 偶氮基、炫·幾氧基(alkylcarbonyloxy)、芳叛氧基、烧氧幾 氧基、^乳幾氧基、亞續醯基(sulfinyl)、續基、續酿基 10 (sulfanyl)、矽基、胺甲醯基、芳基、雜環基、烯基、炔基、 硝基、甲醯基、亞硝基、甲酿氧基、異氰基、氰酸鹽基、 異氰酸鹽基、硫氰酸鹽基、異硫氰酸鹽基或氰基。該等基 亦可被取代。又’鄰接之基亦可形成取代或無取代之縮合 環。) 15 式⑴所表示之删烧衍生物: [化 35]A structure of 50 saturated or unsaturated rings. Each of R3G1 to R3G4 is hydrogen, a functional atom, a substituent, an alkoxy group, an aryloxy group, a perfluoroalkyl group, a wholly-depleted oxy group, an amine group, a leuco group, a aryl group, an alkoxy group, an aryloxy group. Aryloxycarbonyl, azo, alkylcarbonyloxy, aryloxy, alkoxyoxy, methoxyl, sulfinyl, contig, decant 10 (sulfanyl), mercapto, amine, mercapto, aryl, heterocyclyl, alkenyl, alkynyl, nitro, indolyl, nitroso, alkoxy, isocyano, cyanate Isocyanate group, thiocyanate group, isothiocyanate group or cyano group. These groups can also be substituted. Further, a contiguous group may form a substituted or unsubstituted condensed ring. 15) Deodorized derivative represented by formula (1): [Chem. 35]
49 (I) 200932709 (式中,R321〜r328&z322各表示氫原子、飽和或不飽和 之烴基、芳香族烴基、雜環基、取代胺基、取代氧硼基、 烷氧基或芳氧基,、γ3。2及z32丨各表示飽和或不飽和之 烴基、芳香族烴基、雜環基、取代胺基、烷氧基或芳氧基, 5 /切與2322亦可互相結合形成縮合環,n表示1~3之整數,當 II在(3-n)為2以上時,R32丨〜尺似、χ302、γ302、2322及2321可相49 (I) 200932709 (wherein R321~r328&z322 each represents a hydrogen atom, a saturated or unsaturated hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a substituted amine group, a substituted boron boron group, an alkoxy group or an aryloxy group. , γ3. 2 and z32 丨 each represent a saturated or unsaturated hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a substituted amino group, an alkoxy group or an aryloxy group, and 5/cut and 2322 may be bonded to each other to form a condensed ring. n represents an integer from 1 to 3, and when II is (3-n) is 2 or more, R32丨~scale, χ302, γ302, 2322, and 2321 can be phased.
同或相異。但’ η為1時,X302、Υ302及r322為甲基,R328為 氫原子或取代氧硼基之化合物,且η為3時不包含Ζ321為甲基 之化合物。) Q 10 式G0所表示之鎵錯合物: [化 36] q3〇< 〉3a——L315 Q302 . (J) [式中,Q3G1及Q302各表示下述式(K)所示之配位子,L315 表示_素原子、取代或無取代之院基、取代或無取代之環 15燒基、取代或無取代之芳基、取代或無取代之雜環基、_〇R(R ^ 為氫原子、取代或無取代之烷基、取代或無取代之環烷基、 取代或無取代之芳基、取代或無取代之雜環基。)、或 _〇_Ga_Q3〇3(Q304)(Q303及 Q304係與 Q301 及 Q302相同)所示之配 位子]。 20 [化 37] 50 200932709Same or different. However, when η is 1, X302, oxime 302 and r322 are a methyl group, R328 is a hydrogen atom or a compound substituted with an oxyboron group, and when η is 3, a compound in which Ζ321 is a methyl group is not contained. Q 10 Formula G0 represents a gallium complex: [Chem. 36] q3 〇 < 〉 3a - L315 Q302 . (J) [wherein, Q3G1 and Q302 each represent a formula represented by the following formula (K) a position, L315 represents a _-atom, a substituted or unsubstituted, a substituted or unsubstituted ring 15 alkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclic group, _〇R (R ^ Is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group.), or _〇_Ga_Q3〇3 (Q304) (Q303 and Q304 are the same as Q301 and Q302). 20 [化37] 50 200932709
(Κ) [式中,環Α301及α3〇2各係可具有取代基之互相縮合的6 員芳環構造。] 该金屬錯合物作為η型半導體的性質強,且電子注入的 5能力大。此外,由於錯合物形成時之生成能量亦低,因此 所形成之金屬錯合物的金屬與配位子間的結合性強固,作 為發光材料的螢光量子效率亦大。 形成式(Κ)之配位子之環a3G1及A3G2的取代基之具體 例’可舉例如:氯、溴、碘、氟等鹵素原子;曱基、乙基、 10丙基、丁基、S-丁基、t_丁基、戊基、己基、庚基、辛基、 十八燒醯基、三氯甲基等取代或無取代之烷基;苯基、萘 基、聯苯基、苯甲醯亞胺酸基、菲基、苐基、芘基、3-曱 笨基、3-甲氧苯基、氟苯基(fluor0phenyl)、3-三氣甲苯基、 3-三氟甲笨基、3_石肖基苯基等取代或無取代之芳基;甲氧 15基、η-丁氧基、t_丁氧基、三氯甲氧基、三氟乙氧基、五氟 丙氧基、2,2,3,3-四敦丙氧基、1,1,1,3,3,3_六氟_2_丙氧基、 6-(全氣乙基)己氧基等取代或無取代之院氧基,本乳基、p-硝基笨氧基、p_t·丁基苯氧基、3-氟苯氧基、五氟苯基、3-二氟甲基笨氧基等取代或無取代之芳氧基,甲硫基、乙硫 51 200932709 基、t-丁硫基、己硫基、辛硫基、三氟甲硫基等取代或無取 代之院硫基;苯硫基、p-墙基苯硫基、P_t_丁基苯硫基、3-氟苯硫基、五氟苯硫基、3-三氟甲基苯硫基等取代或無取 代之芳硫基;氰基、硝基、胺基、甲胺基、二甲胺基、乙 5 胺基、二乙胺基、二丙胺基、二丁胺基、二苯胺基等單或 雙取代胺基;雙(乙醯氧基甲基)胺基、雙(乙醯氧基乙基)胺 基、雙(乙醯氧基丙基)胺基、雙(乙醯氧基丁基)胺基等醯胺 基;羥基、矽烷氧基、醯基、胺甲醯基、曱基胺甲醯基、 二甲基胺曱醯基、乙基胺甲酿基、二乙基胺甲醯基、丙基 〇 10 胺甲醯基、丁基胺甲醯基、苯基胺甲醯基等取代或無取代 之胺甲醯基;羧酸基、磺酸基、醯亞胺基、環戊基、環己 基等環院基;°比咬基、°比唤基、嘴淀基、璉嗪基 (pyridazinyl)、三嗓基、二氫吲哚基、喧淋基、吖咬基、吨 . 略烧基(pyrrolidinyl)、二崎烧基(dioxanyl)、派咬基、醢嗎 15 琳基(morpholidinyl)、六氫咬基(piperazinyl)、味〇坐基、〇夫 Γ 喃基、。塞吩基、噚°坐基、4二η坐基、苯并噚唾基、嗟嗤基、 噻二哇基、苯并嗟°坐基、***基、咪唑基、苯并咪β坐基等 © 雜環基等。又’以上之取代基群亦可結合形成6員芳環或形 成雜環。 2〇 有機EL元件之較佳形態中,輸送電子之領域或陰極與 有機層之界面領域係含有還原性摻雜物。此處,還原性摻 雜物係定義為可將電子輸送性化合物還原之物質。因此, 只要是具有一定還原性者,各種物質皆可使用,例如,可 適當地選用自由下列所構成之群中至少一種物質:鹼金 52 200932709 5 10 15 ❾ 20 屬、鹼土類金屬、稀土類金屬、鹼金屬之氧化物、鹼金廣 之鹵化物、鹼土類金屬之氧化物、鹼土類金屬之豳化物、 稀土類金屬之氧化物或稀土類金屬之鹵化物、鹼金屬之破 酸鹽、鹼土類金屬之碳酸鹽、稀土類金屬之碳酸鹽、鹼金 屬之有機錯合物、鹼土類金屬之有機錯合物、稀土類金廣 之有機錯合物。 又,具體而言,較佳之還原性摻雜物,可舉例如:由 鈉(Na ;工作函數:2.36eV)、鉀(K ;工作函數:2.28eV)、 如(Rb ;工作函數:2.16eV)、及铯(Cs ;工作函數:l.95eV) 所構成之群中至少一種驗金屬;或由約(Ca ;工作函數: 2.9eV)、鳃(Sr ;工作函數:2.0〜2.5eV)、及鋇(Ba ;工作溱 數:2.52eV)所組成之群中至少一鹼土類金屬。以1作禹數 2.9eV以下者特佳。其中,較佳之還原性摻雜物係選自於由 鉀、條及铯所構成之群中至少一種鹼金屬,且較佳者是铷 或铯,最佳者為铯。該等鹼金屬之還原能力特別高,藉由 往電子注入域之較少量的添加,可預期於有機ELs件中發 光亮度之提升及長壽命化。又,工作函數為2 9eV以下之還 原性摻雜物,亦以該等2種以上之鹼金屬的組合為佳,特別 是含有鉋的組合,例如,以铯與鈉、鉋與鉀、鉋與铷,戋 铯與鈉與鉀之組合為佳。藉由含有與铯之級合可有效率 地發揮還原能力,藉由往電子注入域的添加,可預期於^ 機EL元件中發光亮度的提昇及長壽命化。 、 亦可更於陰極與有機層間設置由絕緣體或半導體構成 之電子注人層。藉由此層,可有效防止電_域,提升 53 200932709 電子注入性。只要電子注入層是絕緣性薄媒,因形成更均 質之薄膜’可減少暗點等畫素缺陷。 絕緣體,以選用下列所構成之群之至少一種金屬化合 物為佳:鹼金屬硫族元素化物(chalcogenide)、鹼土類金屬 5硫族元素化物、鹼金屬之_化物、及鹼土類金屬之函化物。 電子注入層若以此等鹼金屬硫族元素化物等所構成,則可 更提升電子注入性,是為良好。具體而言,較佳之驗金屬 硫族元素化物,可舉例如:氧化二鋰(Lho)、氧化鉀(Κ2〇)、 硫化鈉(NaJ)、硒化鈉(Naje)、及氧化鈉(Na2〇);較佳之 10鹼土類金屬硫族元素化物,可舉例如:氧化鈣(Ca〇)、氧化 鋇(BaO)、氧化锶(SrO)、氧化鈹(Be〇)、硫化鋇(BaS)、及袍 化鈣(CaSe)。又,較佳之鹼金屬鹵化物,可舉例如:氟化 鋰(LiF)、氟化鈉(NaF)、氟化鉀(KF)、氟化绝(CsF)、氣化 經(LiCl)、氯化鉀(KC1)及氣化鈉(NaCl)等。又,較佳之鹼土 15類金屬之鹵化物,可舉例如:氟化鈣(CaF2)、氟化鋇(BaF2)、 氟化勰(SrF2)、氟化鎂(MgF2)、氟化鈹(BeF2)等氟化物、或 氟化物以外之函化物。 又,構成電子注入層之半導體,可舉例如:含有鋇 (Ba)、鈣(Ca)、锶(Sr)、镱(Yb)、鋁(A1)、鎵(Ga)、銦(In)、 20 經(Li)、鈉(Na)、錫(Cd)、鎂(Mg)、石夕(Si)、组(Ta)、銻(Sb) 及鋅(Zn)之至少一種元素之氧化物、氮化物或氧化氮化物 等單獨一種或兩種以上之組合。又,構成電子注入層之無 機化合物係以微結晶或非晶質的絕緣性薄膜為佳。 陰極,可使用工作函數小(例如,4eV以下)之金屬、合 200932709 金、電性傳導性化合物、及該等之混合物作為電極物質。 此種電極物質之具體例,可舉例如:納、納_卸合金、鎮、 鋰、鉋、鎂·銀合金、鋁/氧化鋁、鋁/氧化二鋰(Ai/Li2〇)、 5 ❹ 10 15 ❹ 20 鋁/氧化鋰(A〗/LiO)、鋁/氟化鋰(AVUF)、鋁鋰合金、銦、 稀土類金屬等。 陰極可藉由將該等電極物質蒸鍍或濺鍍等製作。 當發光層之發光是由陰極掏取時,對於陰極發光的透 射率係以大於1〇%為佳。又,作為陰極之薄片電阻係以數 百Ω/□以下為佳,又,膜厚通常為1〇ηιη〜ΐμηι,較佳者是 50〜200nm。 一般而言,有機EL元件由於在超薄膜上施加電場,因 此容易產生因制或短路而造成之晝素缺陷。為了防止此 現象,亦可於一對電極間***絕緣性薄膜層。 使用於絕緣層的材料,可舉例如:氧化銘、氣化裡、 氧化鐘、氟化绝、氧化铯、氧化鎂、氟化鎂、氧化妈、氟 化妈、氮化紹、氧化鈦、氧化石夕、氧化鍺、氮切、氮化 硼氧化翻、氧化釕、氧化飢等。亦可使用該等之混合物 或積層物。 製作有機EL元件之方法,係例如,藉由上述材料及方 法,由陽極依序形成必要之層,最後再形成陰極即可。又, 亦可由陰極至陽極之減方式製作有機EL元件。 以下,說明在透光性基板上,依序設置陽極/電洞注入 層/發光層/電子注入層/陰極所構成之有機el元件的製作 例0 55 200932709 育先,在透光性基板上,v 極材料所形成的薄膜,以作錢法或濺锻法形成由陽 置電洞注人層。電洞注入層的 纟★,在此陽極上設 AM 形成係可藉由真空蒸鍍法、 旋轉塗布法、鑄製法、LB法篝士 4 万法進行,但由易得均質膜 且不易產生針孔等觀點來看,古 請 —丄士 乂真空蒸鍍法形成者為佳。 Γ真空祕㈣成電批人層時,其蒸鍍條件係因所使 =之化合物(電洞注人層的材料)、目的之電洞注人層的構造 “有所差異’但—般Ml適當選擇舰源溫度為 50〜45〇C、真空度為1〇-7〜〗(ν3τ 10(Κ) [wherein, each of the cyclic oxime 301 and the α3〇2 may have a 6-membered aromatic ring structure in which the substituents are condensed with each other. The metal complex is strong as an n-type semiconductor and has a large ability to inject electrons. Further, since the energy of formation in the formation of the complex compound is also low, the bond between the metal of the metal complex formed and the ligand is strong, and the fluorescence quantum efficiency as a light-emitting material is also large. Specific examples of the substituent of the ring a3G1 and A3G2 forming the ligand of the formula (Κ) include halogen atoms such as chlorine, bromine, iodine, and fluorine; mercapto, ethyl, 10 propyl, butyl, and S. a substituted or unsubstituted alkyl group such as butyl, t-butyl, pentyl, hexyl, heptyl, octyl, octadecyl decyl or trichloromethyl; phenyl, naphthyl, biphenyl, benzene Formamidine, phenanthryl, fluorenyl, fluorenyl, 3-hydrazino, 3-methoxyphenyl, fluorophenyl (phenyl), 3-trimethyltolyl, 3-trifluoromethyl a substituted or unsubstituted aryl group such as 3—stone phenyl; methoxy-15, η-butoxy, t-butoxy, trichloromethoxy, trifluoroethoxy, pentafluoropropoxy, Substituted or absent of 2,2,3,3-tetradyloxy, 1,1,1,3,3,3-hexafluoro-2-propoxy, 6-(all-gasethyl)hexyloxy Substituted alkoxy, this lactide, p-nitrophenyloxy, p_t·butylphenoxy, 3-fluorophenoxy, pentafluorophenyl, 3-difluoromethyl strepoxy or the like Unsubstituted aryloxy, methylthio, ethylsulfide 51 200932709 base, t-butylthio, hexylthio, octylthio, trifluoromethylthio, etc. Substituted sulfur base; phenylthio, p-wall phenylthio, P_t_butylphenylthio, 3-fluorophenylthio, pentafluorophenylthio, 3-trifluoromethylphenylthio Or unsubstituted arylthio; cyano, nitro, amine, methylamino, dimethylamino, ethyl 5 amine, diethylamino, dipropylamino, dibutylamino, diphenylamine, etc. Or a disubstituted amine group; bis(ethoxymethyl)amino, bis(ethyloxyethyl)amine, bis(ethoxypropyl)amine, bis(ethoxylated butyl) Amino group such as amine group; hydroxy group, decyloxy group, fluorenyl group, amine mercapto group, decylamine carbhydryl group, dimethylamino fluorenyl group, ethyl amide group, diethylamine formamidine Substituted or unsubstituted aminemethanyl group such as propyl hydrazide 10 amine carbhydryl group, butylamine carbhydryl group, phenylamine carbhydryl group; carboxylic acid group, sulfonic acid group, quinone imine group, cyclopentyl group Ring, cyclohexyl, etc. ring base; ° than bite base, ° call base, mouth base, pyridazinyl (pyridazinyl), triterpene, dihydroindenyl, indole, bite base, tons. Pyrrolidinyl, dioxanyl, pie bite, 醢15 Lin (Morpholidinyl), bite-hexahydro-yl (piperazinyl), flavor square sitting group, tetrahydrothiopyranyl square Γ husband. Queenyl, 坐°, 二, 苯, benzoindol, fluorenyl, thiadiazide, benzoxanthyl, triazolyl, imidazolyl, benzimidyl Etc. © Heterocyclic group and the like. Further, the above substituent groups may be combined to form a 6-membered aromatic ring or a heterocyclic ring. In a preferred embodiment of the organic EL device, the field of electron transport or the interface between the cathode and the organic layer contains a reducing dopant. Here, the reducing dopant is defined as a substance which can reduce an electron transporting compound. Therefore, as long as it is a certain reducing property, various substances can be used. For example, at least one of the following groups can be appropriately selected: alkali gold 52 200932709 5 10 15 ❾ 20 genus, alkaline earth metal, rare earth Metal, alkali metal oxide, alkali gold halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide or rare earth metal halide, alkali metal acid salt, alkaline earth A carbonate of a metal, a carbonate of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. Further, specifically, preferred reducing dopants include, for example, sodium (Na; working function: 2.36 eV), potassium (K; working function: 2.28 eV), such as (Rb; working function: 2.16 eV). And 铯 (Cs; work function: l.95eV) at least one of the group of metals; or by (Ca; working function: 2.9eV), 鳃 (Sr; working function: 2.0~2.5eV), And at least one alkaline earth metal in the group consisting of 钡 (Ba; working number: 2.52 eV). It is especially good to use 1 for 2.9 eV or less. Preferably, the reducing dopant is selected from the group consisting of at least one alkali metal consisting of potassium, bar and strontium, and preferably strontium or barium, and most preferably strontium. The alkali metal has a particularly high reducing ability, and the addition of a small amount to the electron injecting region can be expected to increase the luminance and long life of the organic ELs. Further, the reducing dopant having a working function of 2 9 eV or less is preferably a combination of the two or more alkali metals, particularly a combination containing a planer, for example, bismuth and sodium, planing and potassium, planing and The combination of strontium, barium and sodium and potassium is preferred. By including the combination with ruthenium, the reduction ability can be efficiently utilized, and by adding to the electron injection region, it is expected that the luminance of the EL element in the EL element is improved and the lifetime is extended. Further, an electron injecting layer made of an insulator or a semiconductor may be provided between the cathode and the organic layer. With this layer, the _ domain can be effectively prevented, and the electronic injection property of 53 200932709 can be improved. As long as the electron injecting layer is an insulating thin medium, the formation of a more uniform film can reduce pixel defects such as dark spots. The insulator is preferably at least one metal compound selected from the group consisting of an alkali metal chalcogenide, an alkaline earth metal 5 chalcogenide, an alkali metal compound, and an alkaline earth metal. When the electron injecting layer is composed of such an alkali metal chalcogenide or the like, the electron injecting property can be further improved, which is good. Specifically, preferred metal chalcogenides include, for example, lithium dichloride (Lho), potassium oxide (Na 2 ), sodium sulfide (NaJ), sodium selenide (Naje), and sodium oxide (Na 2 〇). Preferred ten alkaline earth metal chalcogenides include, for example, calcium oxide (Ca〇), barium oxide (BaO), strontium oxide (SrO), strontium oxide (Be〇), barium sulfide (BaS), and Robe calcium (CaSe). Further, preferred alkali metal halides include, for example, lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), fluorinated (CsF), vaporized (LiCl), and chlorinated. Potassium (KC1) and sodium (NaCl). Further, preferred halides of the alkaline earth 15 metal include, for example, calcium fluoride (CaF2), barium fluoride (BaF2), barium fluoride (SrF2), magnesium fluoride (MgF2), and barium fluoride (BeF2). A complex other than fluoride or fluoride. Further, the semiconductor constituting the electron injecting layer may, for example, contain barium (Ba), calcium (Ca), strontium (Sr), ytterbium (Yb), aluminum (Al), gallium (Ga), indium (In), or Oxides, nitrides of at least one element of (Li), sodium (Na), tin (Cd), magnesium (Mg), shi (Si), group (Ta), bismuth (Sb), and zinc (Zn) Or oxynitride or the like alone or in combination of two or more. Further, the inorganic compound constituting the electron injecting layer is preferably a microcrystalline or amorphous insulating film. As the cathode, a metal having a small work function (e.g., 4 eV or less), 200932709 gold, an electrically conductive compound, and a mixture thereof may be used as the electrode material. Specific examples of such an electrode material include, for example, nano, nano-unloaded alloy, town, lithium, planer, magnesium-silver alloy, aluminum/alumina, aluminum/lithium oxide (Ai/Li2〇), 5 ❹ 10 15 ❹ 20 Aluminum / lithium oxide (A / LiO), aluminum / lithium fluoride (AVUF), aluminum lithium alloy, indium, rare earth metals. The cathode can be produced by vapor deposition or sputtering of the electrode material. When the luminescence of the luminescent layer is extracted by the cathode, the transmittance for cathodoluminescence is preferably greater than 1%. Further, the sheet resistance of the cathode is preferably several hundred Ω/□ or less, and the film thickness is usually from 1 〇ηηη to ΐμηι, preferably from 50 to 200 nm. In general, since an organic EL element applies an electric field to an ultrathin film, it is easy to cause a defect of a halogen due to a short circuit or a short circuit. In order to prevent this, an insulating thin film layer may be interposed between a pair of electrodes. The material used for the insulating layer may, for example, be oxidized, vaporized, oxidized, fluorinated, cerium oxide, magnesium oxide, magnesium fluoride, oxidized mother, fluorinated mother, nitriding, titanium oxide, oxidized. Shi Xi, yttrium oxide, nitrogen cutting, boron oxide oxidation, bismuth oxide, oxidative hunger and so on. Mixtures or laminates of these may also be used. The method of producing an organic EL element is, for example, by forming the necessary layer sequentially from the anode by the above materials and methods, and finally forming a cathode. Further, an organic EL device can also be produced by subtracting the cathode to the anode. Hereinafter, a production example of an organic EL element comprising an anode/hole injection layer/light-emitting layer/electron injection layer/cathode on a light-transmissive substrate will be described. 0 55 200932709 First, on a light-transmissive substrate, v The film formed by the pole material is formed into a layer of a positive hole by a method of money or splash forging. The hole in the hole injection layer, the AM formation system on the anode can be carried out by vacuum evaporation method, spin coating method, casting method, LB method, gentleman 40,000 method, but it is easy to produce a homogenous film and is not easy to produce a needle. From the point of view of the hole, etc., it is better to form the ancient vapor-former vacuum vapor deposition method. When the vacuum is secreted (4) into the electric batch, the evaporation conditions are “different” due to the composition of the compound (the material of the hole injection layer) and the purpose of the hole injection layer. Appropriate selection of ship source temperature is 50~45〇C, vacuum degree is 1〇-7~〗 (ν3τ 10
1() ¥、蒸鍍速度為0.01〜5〇nm/ 秒、基板溫度為-50〜30(TC者為佳。 /著,於電職人層上設置發光層。發光層的形成亦 可藉由真空蒸鑛法、職法、旋轉塗布法、鱗製法等方法 將發光材料薄膜化而形成,但由易得均質膜且不易產生針 孔等觀點來看,以真空蒸鑛法形成者為佳。藉由真空蒸鑛 15法形成發光層時,其蒸鑛條件係因所使用之化合物而有所1() ¥, the evaporation rate is 0.01~5〇nm/sec, and the substrate temperature is -50~30 (the TC is better. /, the luminescent layer is provided on the electric person layer. The formation of the luminescent layer can also be The luminescent material is formed by a method such as a vacuum distillation method, a method, a spin coating method, or a scale method. However, it is preferable to form a vacuum vapor deposition method from the viewpoint that a homogeneous film is easily obtained and pinholes are less likely to occur. When the luminescent layer is formed by the vacuum distillation method, the smelting conditions are due to the compound used.
差異,但一般而言,可由與形成電洞注入層相同之條件範 圍内來進行選擇。 然後,於發光層上設置電子注入層。此時亦與電洞注 入層、發光層相同,因為必需得到均質膜,而以藉由真空 2〇蒸鍍法形成者為佳。蒸鍍條件係可由與電洞注入層、發光 層之相同條件範圍内來進行選擇。 最後,將陰極予以積層,可得有機EL元件。陰極係可 藉由蒸鍍法、濺鍍法形成。為了保護基層的有機物層在製 膜時不跫損傷,以真空蒸鍍法為佳。 56 200932709 次的抽真空,由陽 以上有機EL元件的製作,以藉由— 極至陰極一貫作業製作者為佳。 有機EL元件各層之形成方法縣特舰定。含有本發 明之化合物的有機薄膜層可藉由下心所周知的方法形 5成:真2蒸鍍法、分子線蒸鑛法(咖法)、或將本發明之 化合物溶解於_之溶液浸潰法、旋轉塗布法、禱製法、 棒材塗布(bar-coating)法、滾輪塗布法等塗布法。 [實施例]The difference, but in general, can be selected within the same range of conditions as the formation of the hole injection layer. Then, an electron injecting layer is provided on the light emitting layer. At this time, it is also the same as the hole injection layer and the light-emitting layer. Since it is necessary to obtain a homogeneous film, it is preferable to form it by vacuum vapor deposition. The vapor deposition conditions can be selected within the same conditions as those of the hole injection layer and the light-emitting layer. Finally, the cathode is laminated to obtain an organic EL element. The cathode system can be formed by a vapor deposition method or a sputtering method. In order to protect the organic layer of the base layer from damage during film formation, a vacuum evaporation method is preferred. 56 200932709 times of vacuuming, the production of organic EL elements from above and above is better for those who work from the extreme to the cathode. The method for forming each layer of the organic EL element is determined by the county. The organic thin film layer containing the compound of the present invention can be formed by a method known in the art: true 2 vapor deposition method, molecular line steaming method (coffee method), or solution in which the compound of the present invention is dissolved in _ Coating methods such as a method, a spin coating method, a prayer method, a bar-coating method, and a roll coating method. [Examples]
以下,依據實施例更具體地說明本發明。 1〇 合成例1 [5-溴苯并[c]菲之合成] 依照以下之合成圖解合成5_溴苯并[c]菲。 [化 38]Hereinafter, the present invention will be more specifically described based on examples. 1〇 Synthesis Example 1 Synthesis of [5-bromobenzo[c]phenanthrene] 5-Bromobenzo[c]phenanthrene was synthesized according to the following synthesis scheme. [化38]
0HC. (H0)2B-0HC. (H0)2B-
Pd(PPh3)4 Νθ2〇0 DMEPd(PPh3)4 Νθ2〇0 DME
MeO^PPh.MeO^PPh.
t-BuOK THFt-BuOK THF
MeO Br Q ch2ci2 15 於氬氣環境氣體下,將1,4-二溴萘230g、2-曱醯苯基硼 酸121g、四(二本膦)|巴(〇)丨8 #加入燒瓶中。於該燒瓶中加 入二甲基醚(DME)2 4L、及2M碳酸鈉水溶液i 2L,加熱加 熱回流(reflux fl0w)攪拌8小時。冷卻至室溫後,去除水層。 以水飽和食鹽水洗淨分離之有機層後,以硫酸鎮使其乾 20燥。過濾硫酸鎂後’濃縮有機層。將所得之殘渣以矽凝膠 管柱層析精製,得到丨_溴_4_(2_甲醯苯基)萘丨7〇g(產率67%)。 於氬氣環境氣體下,將所得之^溴“^孓曱醯苯基)萘 57 200932709MeO Br Q ch2ci2 15 230 g of 1,4-dibromonaphthalene, 121 g of 2-nonylphenylboronic acid, and tetrakis(diphosphine)|bar (〇)丨8# were placed in a flask under an argon atmosphere. Dimethyl ether (DME) 24 L and 2 M aqueous sodium carbonate solution i 2 L were added to the flask, and the mixture was heated under reflux (reflux fl 0w) and stirred for 8 hours. After cooling to room temperature, the aqueous layer was removed. After washing the separated organic layer with water-saturated saline, it was dried by sulfuric acid and dried. After filtering the magnesium sulfate, the organic layer was concentrated. The residue thus obtained was purified by hydrazine gel column chromatography to give y-bromo-4-(2-pyridinylphenyl)naphthoquinone 7 g (yield: 67%). The resulting bromine "^ phenyl" naphthalene 57 under argon atmosphere gas 2009 2009709
170g、甲氧甲基三苯基氣化^2〇7g、及四氯咬喃(THF)2〇L 裝入燒瓶中。於室溫攪拌時,再於燒瓶中加入t-丁氧鉀 73.6g。再於室溫下攪拌2小時後,加入水151^。以二***抽 出反應溶液’去除水層。以水、飽和食鹽水洗淨分離之有 5機層後’以硫酸鎂使其乾燥。過濾硫酸鎂後,濃縮有機層。 將所得之殘渣以矽凝膠管柱層析精製,得到1-溴·4-[1-(2- 曱氧基乙烯基)苯基]萘180g(產率99%)。 於所得之1-溴·4-[1-(2-曱氧基乙烯基)苯]萘I80g中,加170 g, methoxymethyltriphenyl gasification, 2 g, 7 g, and tetrachloromethane (THF) 2 〇 L were placed in a flask. While stirring at room temperature, 73.6 g of t-butoxy potassium was further added to the flask. After stirring at room temperature for 2 hours, water 151 was added. The reaction solution was extracted with diethyl ether to remove the aqueous layer. After washing and separating with 5 layers of water and saturated saline, the mixture was dried with magnesium sulfate. After filtering magnesium sulfate, the organic layer was concentrated. The residue thus obtained was purified by hydrazine gel column chromatography to give 1-bromo 4-[1-(2- decyloxy)phenyl]naphthalene 180 g (yield: 99%). In the obtained 1-bromo-4-[1-(2-decyloxyvinyl)benzene]naphthalene I80g, added
入二氣甲從UL ’再於室溫下攪拌時加入甲磺酸25mL。持 10續於室溫下欖拌8小時。於反應結束後加入1〇%碳酸鉀水溶 液1L。去除水層。以水、飽和食鹽水洗淨分離之有機層後, 以硫酸鎂使其乾燥。過濾硫酸鎂後,濃縮有機層。將所得 之殘渣以矽凝膠管柱層析精製,得到5-溴苯并[c]菲24.4g(產 率 15%)。 15 實施例1When the second gas was added from UL' and stirred at room temperature, 25 mL of methanesulfonic acid was added. Hold 10 for 8 hours at room temperature. After the end of the reaction, 1 L of a 1% potassium carbonate aqueous solution was added. Remove the water layer. The separated organic layer was washed with water and saturated brine and dried over magnesium sulfate. After filtering magnesium sulfate, the organic layer was concentrated. The residue thus obtained was purified by hydrazine gel column chromatography to give 2-bromobenzo[c]phenanthrene 24.4 g (yield: 15%). 15 Example 1
依·照以下之合成圖解合成化合物卜 [化 39]According to the following synthesis diagram, the compound is synthesized [Chem. 39]
甲苯 氬氣環境氣體下’於合成例1中調製之5_溴苯并[c]菲 3.07g中’加入以眾所周知的方法合成的1〇_(2•蔡)葱_9,酸 4.18g、四(三苯膦)鈀⑼〇 231g、甲苯4〇mL、及说碳酸鈉水 58 200932709 溶液20mL,回流攪拌8小時。冷卻至室溫後,以曱苯抽出 反應溶液。去除水層,再以水、飽和食鹽水依序洗淨分離 後之有機層後,以硫酸鎂使其乾燥。過濾硫酸鎂後,濃縮 有機層。將所得之殘渣以矽凝膠管柱層析精製,得到淡黄 5 色結晶4.13g。質譜分析的結果,確認所得之結晶係前述化 合物1。化合物1相對於分子量530.20,111/6=530。 實施例2 依照以下之合成圖解合成化合物2。Under the toluene argon atmosphere, '5-bromobenzo[c]phenanthrene 3.07 g prepared in Synthesis Example 1 was added to 1 〇_(2•蔡) onion _9 synthesized by a well-known method, acid 4.18 g, Tetrakis(triphenylphosphine)palladium (9) ruthenium 231 g, toluene 4 〇 mL, and sodium carbonate water 58 200932709 solution 20 mL, and stirred under reflux for 8 hours. After cooling to room temperature, the reaction solution was extracted with benzene. The aqueous layer was removed, and the separated organic layer was washed successively with water and saturated brine, and dried over magnesium sulfate. After filtering magnesium sulfate, the organic layer was concentrated. The obtained residue was purified by hydrazine gel column chromatography to yield 4.13 g of pale yellow color crystals. As a result of mass spectrometry, it was confirmed that the obtained crystal was the above compound 1. Compound 1 was relative to a molecular weight of 530.20, 111/6 = 530. Example 2 Compound 2 was synthesized according to the following synthesis scheme.
[化 40][40]
15 除了使用以眾所周知的方法合成之10-(9-菲基)蔥-9-硼 酸取代10-(2-萘)蔥-9-硼酸以外,與實施例1同樣地合成,得 到結晶。質譜分析的結果,確認所得之結晶係化合物2。化 合物2相對於分子量580.22,m/e=580。 實施例3 20 依照以下之合成圖解合成化合物3。 [化 41] 59 200932709In the same manner as in Example 1, except that 10-(2-phenanthryl) onion-9-boronic acid which was synthesized by a well-known method was used in place of 10-(2-naphthalene) onion-9-boronic acid, crystallization was obtained. As a result of mass spectrometry, the obtained crystalline compound 2 was confirmed. Compound 2 had a molecular weight of 580.22 and m/e = 580. Example 3 20 Compound 3 was synthesized according to the following synthesis scheme. [Chem. 41] 59 200932709
除了使用以眾所周知的方法合成之10-苯蔥-9-硼酸取 代10-(2-萘)蔥-9-硼酸以外,與實施例1同樣地合成,得到結 晶。質譜分析的結果,確認所得之結晶係化合物3。化合物 3相對於分子量480.19,111乂=480。 10 實施例4 依照以下之合成圖解合成化合物4。 [化 42]Crystallization was carried out in the same manner as in Example 1 except that 10-benzoate-9-boronic acid synthesized by a well-known method was used instead of 10-(2-naphthalene) onion-9-boronic acid. As a result of mass spectrometry, the obtained crystalline compound 3 was confirmed. Compound 3 has a molecular weight of 480.19, 111 乂 = 480. 10 Example 4 Compound 4 was synthesized according to the following synthesis scheme. [化42]
除了使用以眾所周知的方法合成之10-(2-聯苯)蔥-9-硼 酸取代10-(2-萘)蔥-9-硼酸以外,與實施例1同樣地合成,得 20 到結晶。質譜分析的結果,確認所得之結晶係化合物4。化 合物4相對於分子量556.22,m/e=556。 實施例5 依照以下之合成圖解合成化合物5。 [化 43] 60 200932709The synthesis was carried out in the same manner as in Example 1 except that 10-(2-biphenyl) onion-9-boronic acid synthesized by a well-known method was used in place of 10-(2-naphthalene) onion-9-boronic acid to obtain 20 crystals. As a result of mass spectrometry, the obtained crystalline compound 4 was confirmed. Compound 4 had a molecular weight of 556.22 and m/e = 556. Example 5 Compound 5 was synthesized according to the following synthesis scheme. [化43] 60 200932709
除了使用以眾所周知的方法合成之10-(3-聯苯)蔥-9-硼 酸取代10-(2-萘)蔥-9-硼酸以外,與實施例1同樣地合成,得 到結晶。質譜分析的結果,確認所得之結晶係化合物5。化 合物5相對於分子量556.22,m/e=556。 10 實施例6 依照以下之合成圖解合成化合物6。 [化 44]Crystallization was carried out in the same manner as in Example 1 except that 10-(3-biphenyl) onion-9-boronic acid was synthesized by a well-known method, and 10-(2-naphthalene) onion-9-boronic acid was used. As a result of mass spectrometry, the obtained crystalline compound 5 was confirmed. Compound 5 had a molecular weight of 556.22 and m/e = 556. 10 Example 6 Compound 6 was synthesized according to the following synthesis scheme. [化44]
Na2C03aq ❿ 甲笨 除了使用以眾所周知的方法合成之10-(4-聯苯)蔥-9-硼 酸取代10-(2-萘)蔥-9-硼酸以外,與實施例1同樣地合成,得 到結晶。質譜分析的結果,確認所得之結晶係化合物6。化 20 合物6相對於分子量556.22,m/e=556。 實施例7 依照以下之合成圖解合成化合物7。 [化 45] 61 200932709Na2C03aq 甲 was synthesized in the same manner as in Example 1 except that 10-(4-biphenyl) onion-9-boronic acid was synthesized by a well-known method, and 10-(2-naphthalene) onion-9-boric acid was used to obtain crystals. . As a result of mass spectrometry, the obtained crystalline compound 6 was confirmed. The compound 6 was relative to a molecular weight of 556.22, m/e = 556. Example 7 Compound 7 was synthesized according to the following synthesis scheme. [化45] 61 200932709
除了使用以眾所周知的方法合成之l〇-[3-(l-萘)苯基] 蔥-9-硼酸取代10-(2-萘)蒽-9-硼酸以外,與實施例1同樣地 合成,得到結晶。質譜分析的結果,確認所得之結晶係化 合物7。化合物7相對於分子量606.23,111/6=606。 10 實施例8 依照以下之合成圖解合成化合物8。 [化 46]It was synthesized in the same manner as in Example 1 except that 10-(2-(1-naphthyl)phenyl] onion-9-boronic acid was synthesized by a well-known method, and 10-(2-naphthalene)-9-boronic acid was used. Crystallization is obtained. As a result of mass spectrometry, the obtained crystalline compound 7 was confirmed. Compound 7 has a molecular weight of 606.23, 111/6 = 606. 10 Example 8 Compound 8 was synthesized according to the following synthesis scheme. [Chem. 46]
除了使用以眾所周知的方法合成之1〇-[3-(2-萘)苯基] 蔥-9-硼酸取代10-(2-萘)蔥-9-硼酸以外,與實施例1同樣地 20 合成,得到結晶。質譜分析的結果,確認所得之結晶係化 合物8。化合物8相對於分子量606.23,m/e=606。 實施例9 依照以下之合成圖解合成化合物9。 [化 47] 62 20093270920 Synthesis was carried out in the same manner as in Example 1 except that 1-(2-(2-naphthalene)phenyl] onion-9-boronic acid was synthesized by a well-known method in place of 10-(2-naphthalene) onion-9-boronic acid. , get crystallized. As a result of mass spectrometry, the obtained crystalline compound 8 was confirmed. Compound 8 has a molecular weight of 606.23 and m/e = 606. Example 9 Compound 9 was synthesized according to the following synthesis scheme. [化47] 62 200932709
除了使用以眾所周知的方法合成之10-[4-(2-萘)苯]蔥 -9-硼酸取代10-(2-萘)蔥-9-硼酸以外,與實施例1同樣地合 成,得到結晶。質譜分析的結果,確認所得之結晶係化合 ® 物9。化合物9相對於分子量606.23,m/e=606。 10 實施例10 依照以下之合成圖解合成化合物10。 - [化 48]Synthesis was carried out in the same manner as in Example 1 except that 10-[4-(2-naphthalene)benzene] onion-9-boronic acid was synthesized by a well-known method, and 10-(2-naphthalene) onion-9-boronic acid was used. . As a result of mass spectrometry, it was confirmed that the obtained crystalline compound was 9 . Compound 9 has a molecular weight of 606.23 and m/e = 606. 10 Example 10 Compound 10 was synthesized according to the following synthesis scheme. - [48]
1515
Na2C03aq 甲苯Na2C03aq toluene
除了使用以眾所周知的方法合成之10-[4-(1-萘)苯基] 蔥-9-硼酸取代10-(2-萘)蔥-9-硼酸以外,與實施例1同樣地 合成,得到結晶。質譜分析的結果,確認所得之結晶係化 20 合物10。化合物10相對於分子量606.23,m/e=606。 合成例2 [5-(3-溴苯基)苯并[c]菲之合成] 依照以下之合成圖解合成5-(3-溴苯基)苯并[c]菲。 [化 49] 63 200932709It was synthesized in the same manner as in Example 1 except that 10-[4-(1-naphthalene)phenyl] onion-9-boronic acid synthesized by a well-known method was used instead of 10-(2-naphthalene) onion-9-boronic acid. crystallization. As a result of mass spectrometry, the obtained crystallized compound 10 was confirmed. Compound 10 has a molecular weight of 606.23 and m/e = 606. Synthesis Example 2 Synthesis of [5-(3-bromophenyl)benzo[c]phenanthrene] 5-(3-Bromophenyl)benzo[c]phenanthrene was synthesized according to the following synthesis scheme. [化49] 63 200932709
5 於氬氣環境氣體下,將合成例1中調製之5-溴苯并[c] 菲lO.lg裝入燒瓶中’再加入脫水謎400mL。將反應溶液冷 卻至-40°C,加入1.6M之n-丁基鋰的己烷溶液22此後,升溫 至0°C ’攪拌1小時。將反應溶液冷卻至_6〇°c後,滴入硼酸 三異丙酯14.4g之脫水醚10mL。一面升溫至室溫一面持續擾 ❹ 10 拌反應溶液5小時。加入10%之鹽酸水溶液i〇〇mL,授拌1 小時。去除水層,以水、飽和食鹽水洗淨分離之有機層後, 以硫酸鎖使其乾燥。過遽硫酸鎮後,濃縮有機層。將所得 之固體以己烷洗淨,得到苯并[c]菲-5-硼酸5.37g(產率60%)。 , 於風氣環境氣體下,將所得之苯并[〇]菲_5·棚酸3.26g、 15 3_溴破苯2.83g、四(三苯膦)纪(〇)〇.231g、曱苯4〇mL及2M碳 酸鈉水溶液2〇mL裝入燒瓶中’回流攪拌8小時。冷卻至室 溫後’以甲苯抽出反應溶液。去除水層。以水、飽和食鹽 〇 水依序洗淨分離之有機層後,以硫酸鎂使其乾燥。過遽硫 酸錄後’濃縮有機層。將所得之殘潰以石夕凝膠管检層析精 20製,得到10-(3-漠苯基)苯并[C]菲3.64g(95%)。 實施例11 依照以下之合成圖解合成化合物U。 [化 50] 64 200932709 55 5-Bromobenzo[c]phenanthrene 10 lg prepared in Synthesis Example 1 was placed in a flask under an argon atmosphere gas, and then 400 mL of a dehydration puzzle was added. The reaction solution was cooled to -40 ° C, and 1.6 M of a n-butyllithium hexane solution 22 was added thereto, and the mixture was heated to 0 ° C and stirred for 1 hour. After cooling the reaction solution to _6 ° C, a solution of 14.4 g of triisopropyl borate (10 mL) was added dropwise. Continue to disturb the temperature while warming to room temperature. 10 Mix the reaction solution for 5 hours. Add 10% hydrochloric acid aqueous solution i〇〇mL and mix for 1 hour. The aqueous layer was removed, and the separated organic layer was washed with water and saturated brine, and dried with sulfuric acid. After passing through the sulfuric acid town, the organic layer was concentrated. The obtained solid was washed with hexane to obtain 5.37 g of benzo[c]phenanthrene-5-boronic acid (yield: 60%). Under the atmosphere gas, the obtained benzo[〇]phenanthrene _5· shed acid 3.26g, 153 bromine benzene 2.83g, tetrakis(triphenylphosphine) 〇.231g, benzene 4 2 mL of 〇mL and 2M aqueous sodium carbonate solution were placed in a flask and stirred under reflux for 8 hours. After cooling to room temperature, the reaction solution was extracted with toluene. Remove the water layer. The separated organic layer was washed successively with water and saturated brine and then dried over magnesium sulfate. After the sulphuric acid was recorded, the organic layer was concentrated. The resulting residue was purified by Shih-Gel gel chromatography to give 10-(3-diphenylphenyl)benzo[C]phenanthrene 3.64 g (95%). Example 11 Compound U was synthesized according to the following synthesis scheme. [化 50] 64 200932709 5
〇 10 除了使用合成例2中調製之10-(3-溴苯基)苯并[c]菲取 代5-溴苯并[c]菲以外,與實施例1同樣地合成,得到結晶。 質譜分析的結果,確認所得之結晶係化合物11。化合物11 相對於分子量606.23,111/6=606。 實施例12 依照以下之合成圖解合成化合物12。 [化 51] 15 ❿In the same manner as in Example 1, except that 10-(3-bromophenyl)benzo[c]phenanthrenequinone prepared in Synthesis Example 2 was used instead of 5-bromobenzo[c]phenanthrene, crystals were obtained. As a result of mass spectrometry, the obtained crystalline compound 11 was confirmed. Compound 11 was relative to the molecular weight of 606.23, 111/6 = 606. Example 12 Compound 12 was synthesized according to the following synthetic scheme. [化 51] 15 ❿
20 除了使用以眾所周知的方法合成之10-[4-(1-萘)苯基] 蔥-9-硼酸取代10-(2-萘)蔥-9-硼酸以外,與實施例11同樣地 合成,得到結晶。質譜分析的結果,確認所得之結晶係化 合物12。化合物12相對於分子量682.27,m/e=682。 實施例13 [有機EL元件之製作] 將25mm><75mmxl.lmm厚的設置有ITO透明電極之玻 65 200932709 璃基板(Geomatics公司製)於異丙醇中進行超音波洗淨5分 鐘後’進行UV臭氧洗淨30分鐘。將洗淨後之設有透明電極 線的玻璃基板裝設於真空蒸鍍裝置之基板固持部後’首 先,在透明電極線所形成侧的面上,成膜膜厚60nm之由化 5 合物A-1構成的膜(A-1膜),以覆蓋前述透明電極。於成膜 A-1膜後,緊接著於該A-1膜上成膜膜厚20nm之由化合物 A-2構成的膜(A-2膜)。 接著’於A-2膜上,以40 : 2之重量比,將實施例1中調 製之化合物1與芳胺衍生物D-1成膜成膜厚40nm的膜,作為 Θ 1〇 藍色系發光層。 · 於藍色系發光層上’蒸鍍膜厚20nm之化合物Alq並成 膜’作為電子輸送層。之後’將LiF成膜成膜厚1 nm。於該 '20 was synthesized in the same manner as in Example 11 except that 10-[4-(1-naphthalene)phenyl] onion-9-boronic acid was synthesized by a well-known method, and 10-(2-naphthalene) onion-9-boronic acid was used. Crystallization is obtained. As a result of mass spectrometry, the obtained crystalline compound 12 was confirmed. Compound 12 has a molecular weight of 682.27 and m/e = 682. [Example 13] [Production of Organic EL Device] A glass substrate (2009 manufactured by Geomatics Co., Ltd.) having an ITO transparent electrode of 25 mm > 75 mm x 1.1 mm thick was ultrasonically washed in isopropyl alcohol for 5 minutes. Wash with UV ozone for 30 minutes. After the cleaned glass substrate provided with the transparent electrode wire is mounted on the substrate holding portion of the vacuum vapor deposition apparatus, first, a film having a film thickness of 60 nm is formed on the surface on the side where the transparent electrode wire is formed. A film (A-1 film) composed of A-1 covers the transparent electrode. Immediately after the film formation of the A-1 film, a film (A-2 film) composed of the compound A-2 having a film thickness of 20 nm was formed on the A-1 film. Then, the compound 1 prepared in Example 1 and the arylamine derivative D-1 were formed into a film having a film thickness of 40 nm on a film of A-2 at a weight ratio of 40:2, and used as a ruthenium blue film. Light-emitting layer. On the blue light-emitting layer, a compound Alq having a thickness of 20 nm was deposited and formed into a film as an electron transport layer. Thereafter, LiF was deposited into a film thickness of 1 nm. At the '
LiF膜上蒸鑛150nm之金屬A1 ’形成金屬陰極,而形成有機 EL元件。 15 [化 52]On the LiF film, a 150 nm metal A1' was formed to form a metal cathode to form an organic EL element. 15 [化52]
A-1A-1
66 20093270966 200932709
5 ❿ 10 測定製作完成之有機EL元件於電流密度lOmA/cm2之 驅動時的發光效率、及初期亮度lOOOnit、室溫、DC定電流 驅動下之發光半衰期。於表1顯示結果。 實施例14-24 除了使用表1之化合物取代化合物1作為主體材料以 外,與實施例13同様地製作有機EL元件,並評價。於表1 顯示結果。 比較例1 除了使用化合物B取代化合物1以外,與實施例13同様 地製作有機EL元件,並評價。於表1顯示結果。 [化 53]5 ❿ 10 The luminous efficiency of the organic EL element produced by driving at a current density of 10 mA/cm 2 and the initial half-life of the initial luminance of 1000 nit, room temperature, and DC constant current were measured. The results are shown in Table 1. [Example 14-24] An organic EL device was produced and evaluated in the same manner as in Example 13 except that the compound of Table 1 was used instead of the compound 1 as a host material. The results are shown in Table 1. Comparative Example 1 An organic EL device was produced and evaluated in the same manner as in Example 13 except that Compound B was used instead of Compound 1. The results are shown in Table 1. [化53]
15 化合物B 比較例2 除了使用化合物C取代化合物1以外,與實施例13同様 地製作有機EL元件,並評價。於表1顯示結果。 [化 54] 67 20093270915 Compound B Comparative Example 2 An organic EL device was produced and evaluated in the same manner as in Example 13 except that Compound C was used instead of Compound 1. The results are shown in Table 1. [化54] 67 200932709
比較例3 除了使用化合物D取代化合物1以外,與實施例13同様 5 地製作有機EL元件,並評價。於表1顯示結果。 [化 55]Comparative Example 3 An organic EL device was produced and evaluated in the same manner as in Example 13 except that the compound D was used instead of the compound 1. The results are shown in Table 1. [化55]
P Η bP Η b
化合物DCompound D
[表1] 主體 摻雜物 發光效率 (cd/A) 半衰期 ㈣ 實施例13 化合物1 化合物D-1 6.5 7000 實施例14 化合物2 化合物D-1 6.5 7000 實施例15 化合物3 化合物D-1 6.7 7000 實施例16 化合物4 化合物D-1 6.7 7000 實施例17 化合物5 化合物D-1 6.7 7000 實施例18 化合物6 化合物D-1 6.7 7000 實施例19 化合物7 化合物D-1 6.7 8000 實施例20 化合物8 化合物D-1 6.7 8000 實施例21 化合物9 化合物D-1 6.7 8000 實施例22 化合物10 化合物D-1 6.7 8000 實施例23 化合物11 化合物D-1 7.2 8000 實施例24 化合物12 化合物D-1 7.2 8000 比較例1 化合物B 化合物D-1 6.0 4000 比較例2 化合物C 化合物D-1 6.4 5000 比較例3 化合物D 化合物D-1 3.2 100 68 200932709 由實施例及比較例,可確認使用本發明之縮合芳香族 衍生物的有機EL元件係長壽命,且高效率。特別是,於比 較實施例13〜24與比較例3時,可知本發明之縮合芳香環衍 生物相較於含有胺基的化合物D,對電洞、電子之耐性強, 5 係非常長壽之材料。 實施例25 依照以下之合成圖解合成化合物13。 [化 56][Table 1] Main body dopant luminous efficiency (cd/A) Half-life (IV) Example 13 Compound 1 Compound D-1 6.5 7000 Example 14 Compound 2 Compound D-1 6.5 7000 Example 15 Compound 3 Compound D-1 6.7 7000 Example 16 Compound 4 Compound D-1 6.7 7000 Example 17 Compound 5 Compound D-1 6.7 7000 Example 18 Compound 6 Compound D-1 6.7 7000 Example 19 Compound 7 Compound D-1 6.7 8000 Example 20 Compound 8 Compound D-1 6.7 8000 Example 21 Compound 9 Compound D-1 6.7 8000 Example 22 Compound 10 Compound D-1 6.7 8000 Example 23 Compound 11 Compound D-1 7.2 8000 Example 24 Compound 12 Compound D-1 7.2 8000 Comparison Example 1 Compound B Compound D-1 6.0 4000 Comparative Example 2 Compound C Compound D-1 6.4 5000 Comparative Example 3 Compound D Compound D-1 3.2 100 68 200932709 From the examples and comparative examples, it was confirmed that the condensed aromatic compound of the present invention was used. The organic EL device of the derivative has a long life and high efficiency. In particular, when Comparative Examples 13 to 24 and Comparative Example 3 were compared, it was found that the condensed aromatic ring derivative of the present invention is more resistant to holes and electrons than the compound D containing an amine group, and the material having a very long life of 5 series . Example 25 Compound 13 was synthesized according to the following synthesis scheme. [化56]
化合物13 (1) 2-苯蔥之合成 於氬氣環境氣體下,裝入苯硼酸14.5g、2-溴蔥25.7g、 四(三苯膦)鈀(0)4.62g、甲苯400mL、2M碳酸鈉水溶液 20 200mL,回流攪拌8小時。冷卻至室溫後,過濾取出析出之 結晶。使用甲苯-己烷重複將個體再結晶、洗淨後,得到2-苯蔥19.1g(產率75%)。 (2) 9,10-二溴-2-苯蔥之合成 使2-苯蔥19.1g於Ν,Ν-二甲基甲醯胺200mL中加熱溶 69 200932709 解,加入Ν·溴破珀酿亞胺29.4g之N,N-二甲基甲醯胺2〇mL 溶液後,以6(TC加熱攪拌6小時。冷卻至室溫後’將反應溶 液注入1L之水中。將所得之個體以甲醇、水、曱醇依序洗 淨,以曱苯-己烷重複再結晶、洗淨,得到9,1〇-二溴-2-苯蔥 5 24.8g(產率 80%)。 (3)化合物13之合成 於氬氣環境氣體下,裝入9,10-二溴-2-苯蔥2.06g、苯并Compound 13 (1) Synthesis of 2-Penyl onion under argon atmosphere, 14.5 g of phenylboronic acid, 25.7 g of 2-bromo onion, 4.62 g of tetrakis(triphenylphosphine)palladium (0), 400 mL of toluene, 2M carbonate 20 200 mL of a sodium aqueous solution was stirred under reflux for 8 hours. After cooling to room temperature, the precipitated crystals were taken out by filtration. The individual was recrystallized and washed with toluene-hexane, and 19.1 g of 2-phenyl onion was obtained (yield 75%). (2) Synthesis of 9,10-dibromo-2-phenyl onion The 19.1 g of 2-phenyl onion was heated and dissolved in 200 mL of hydrazine and dimethyl-dimethylformamide. 200932709 Solution, added Ν· Bro Bropo After a solution of 29.4 g of N,N-dimethylformamide in 2 mL of amine, the mixture was stirred with 6 (TC for 6 hours. After cooling to room temperature, the reaction solution was poured into 1 L of water. The obtained individual was methanol, Water and sterol were washed sequentially, and recrystallized and washed with terpene-hexane to obtain 9,2 〇-dibromo-2-phenyl onion 5 24.8 g (yield 80%). (3) Compound 13 The synthesis was carried out under an argon atmosphere, and charged with 9,10-dibromo-2-phenyl onion 2.06 g, benzo
[c]菲-5-硼酸2.52g、四(三苯膦)鈀(〇)〇.231g、甲苯40mL、2M 碳酸納水溶液20mL,回流攪拌8小時。冷卻至室溫後,過 1〇濾析出之結晶。將所得之結晶以甲醇、水、甲醇洗淨後, 以甲苯再結晶’得到黄色結晶4.59g。質譜分析之結果,該 為目標物’相對於分子量706.27,m/e=706。 實施例26 依‘、、以下之合成圖解合成化合物14。 15 [化 57][c] phenanthrene-5-boric acid 2.52 g, tetrakis(triphenylphosphine)palladium(〇)〇.231 g, toluene 40 mL, 2M aqueous sodium carbonate solution 20 mL, and stirred under reflux for 8 hours. After cooling to room temperature, the crystals were separated by filtration. The obtained crystals were washed with methanol, water and methanol, and then recrystallized from toluene to give 4.59 g of yellow crystals. As a result of mass spectrometry, this was the target ' relative to the molecular weight of 706.27, m/e = 706. Example 26 Compound 14 was synthesized according to the following synthesis scheme. 15 [化57]
Pd(PPh3)4 Na2C〇3aq 甲苯Pd(PPh3)4 Na2C〇3aq toluene
化合物14 200932709 (1) 4-[苯并[c]菲-5-基]苯硼酸之合成 於氩氣環境氣體下,將10-(4-溴苯基)苯并[c]菲7.66g裝 入燒瓶中,再添加脫水fe|400mL。將反應溶液冷卻至-40°C, 再添加1.6M之η-丁基鐘之己烧溶液i4mL ’升溫至〇。(:後,Compound 14 200932709 (1) Synthesis of 4-[benzo[c]phenanthr-5-yl]benzeneboronic acid in an argon atmosphere, 10-(4-bromophenyl)benzo[c]phenanthrene 7.66 g Into the flask, add dehydrated fe|400mL. The reaction solution was cooled to -40 ° C, and a 1.6 M η-butyl hexane solution i4 mL was added to raise the temperature to hydrazine. (:Rear,
5攪拌1小時。將反應溶液冷卻至-6(TC後,滴入溶解之脫水 醚20mL溶液至硼酸三異丙酯9.41g« —面將反應溶液升溫至 室溫一面持續攪拌5小時。添加1〇%之鹽酸水溶液1〇〇m;L, 再攪拌1小時。去除水層後,以水、飽和食鹽水洗淨分離之 有機層後,以硫酸鎂使其乾燥。過濾硫酸鎂後,濃縮有機 1〇層。以己烷洗淨所得之固體,得到4-[苯并[c]菲-5-基]苯硎 酸4.18g(產率 60%)。 (2) 化合物14之合成 化合物13之合成中,使用4_[苯并[(;]菲_5基]苯硼酸取 代苯并[c]菲-5-硼酸,以同様之方法合成。質譜分析之結 15果,該為目標物,相對於分子量858.33,m/e=858。 實施例27 依照以下之合成圖式合成化合物15。 [化 58] 71 2009327095 stir for 1 hour. After cooling the reaction solution to -6 (TC, the solution of the dissolved dehydrated ether 20 mL was added dropwise to 9.41 g of triisopropyl borate. The reaction solution was allowed to warm to room temperature while stirring for 5 hours. Add 1% aqueous hydrochloric acid solution. After the water layer was removed, the separated organic layer was washed with water and saturated brine and dried over magnesium sulfate. After filtered over magnesium sulfate, the organic layer was concentrated. The obtained solid was washed with hexane to obtain 4.18 g (yield: 60%) of 4-[benzo[c]phenanthr-5-yl]benzoic acid. (2) Synthesis of Compound 14 Compound 14 was used. [Benzo[(;)phenanthroline-5-phenylboronic acid-substituted benzo[c]phenanthrene-5-boronic acid, synthesized by the same method. Mass spectrometry analysis of the fruit, which is the target, relative to the molecular weight of 858.33, m /e = 858. Example 27 Compound 15 was synthesized according to the following synthesis scheme. [Chem. 58] 71 200932709
於氬氣環境氣體下,裝入笨并[c]菲_5_硼酸5 98g、2 15溴蔥5.14g、四(三苯膦)把⑼〇.462g、12_二甲氧乙烷Under argon atmosphere, charged with [c] phenanthrene-5-borate 5 98g, 2 15 bromine onion 5.14g, tetrakis (triphenylphosphine) put (9) 〇.462g, 12-dimethoxyethane
2M碳酸鈉水溶液i5mL,回流攪拌8小時。於冷卻至a、、w y 過濾取出析出之結晶。使用甲苯·己烷重複將所得之偏體再 結晶、洗淨後,得到5-(2-蔥基)苯并[c]菲6.07g(產率75%)。 (2)5-(9,10-二溴蔥-2-基)苯并[c]菲之合成 2〇 使5-(2-蔥基)苯并[c]菲6.07g於Ν,Ν-二甲基甲醯胺 100mL中加熱溶解,添加Ν-溴琥珀醯亞胺5.87g之Ν,Ν-二甲 基甲醯胺10mL溶液後,以60°C加熱攪拌6小時。冷卻至室 溫後,將反應溶液注入1L之水中。將所得之個體以甲醇、 水、甲醇依序洗淨後,以甲苯-己烷重複再結晶、洗淨,得 72 200932709 到5-(9’1〇-二溴葱-2_基)苯并邮响(產率8〇%)。 (3)化合物15之合成 於氬氣環境氣體下,裝入⑽,U)-二漠慧-2-基)苯并[c] 菲5.62g、2-萘魏3.78g、四(三笨膦)⑽)〇 462g、甲苯 ❺ 10 15 4〇mL、2M碳酸納水溶液施L,回流擾摔8小時。於冷卻至 室溫後’ i«取出析出之結晶。以甲醇、水、甲醇洗淨所 得之結晶後,以甲苯再結晶,得到黄色結晶42化。質譜分 析之結果,該為目標物,相對於分子量656 25,m/e=656。 實施例28-30 除了使用表2之化合物取代化合物丨作為主體且使用 下述化合物D-2取代芳胺衍生物D]作為摻雜物以外與實 施例13同様地製作有機EL元件。於表丨顯示結果。另外^主 體與摻雜物之比係4〇 : 2(膜厚比)。與實施例坨同樣地,評 價所得之有機EL元件於電流密度心缺〆之驅動時的元 件性能(驅動電壓、發光效率)及半衰期。於表2顯示妗果。 [化 59]2 mL of 2M aqueous sodium carbonate solution was stirred at reflux for 8 hours. The precipitated crystals were taken out by cooling to a, w y . The obtained partial body was recrystallized and washed with toluene·hexane, and then 5-(2- onionyl)benzo[c]phenanthrene was obtained (yield: 75%). (2) Synthesis of 5-(9,10-dibromoin-2-yl)benzo[c]phenanthrene 2〇5-(2-onionyl)benzo[c]phenanthrene 6.07g in Ν,Ν- 100 mL of dimethylformamide was dissolved by heating, and 5.87 g of hydrazine-bromosuccinimide and 10 mL of hydrazine-dimethylformamide were added thereto, followed by heating and stirring at 60 ° C for 6 hours. After cooling to room temperature, the reaction solution was poured into 1 L of water. The obtained individual is washed sequentially with methanol, water and methanol, and then recrystallized and washed with toluene-hexane to obtain 72 200932709 to 5-(9'1〇-dibromo onion-2_yl)benzene. Mail ring (yield 8〇%). (3) Synthesis of compound 15 under argon atmosphere, charged with (10), U)-dimethylene-2-yl)benzo[c]phenanthrene 5.62 g, 2-naphthalene Wei 3.78 g, tetra (triphenylphosphine) (10)) 〇 462g, toluene ❺ 10 15 4 〇 mL, 2M sodium carbonate aqueous solution was applied, and refluxed for 8 hours. The precipitated crystals were taken out after cooling to room temperature. The obtained crystals were washed with methanol, water and methanol, and then recrystallized from toluene to give a crystal. As a result of mass spectrometry analysis, this was the target, m/e = 656 with respect to molecular weight 656 25. Example 28-30 An organic EL device was produced in the same manner as in Example 13 except that the compound of Table 2 was used instead of the compound oxime as a host and the following compound D-2 was used instead of the arylamine derivative D] as a dopant. The results are displayed in the table. In addition, the ratio of the main body to the dopant is 4 〇 : 2 (film thickness ratio). In the same manner as in Example ,, the elemental performance (driving voltage, luminous efficiency) and half-life of the organic EL element obtained by the evaluation of the current density defect were evaluated. The results are shown in Table 2. [化59]
73 200932709 [表2] 主體 摻雜物 電壓 (V) 發光效率 (cd/A) 發光色 壽命 (Hr) 實施例28 化合物13 D-2 6.5 22 綠色 30000 實施例29 化合物14 D-2 6.6 22 綠色 30000 實施例30 化合物15 D-2 6.5 22 綠色 30000 實施例31 化合物13 D-3 6.7 21 綠色 50000 實施例32 化合物14 D-3 6.7 21 綠色 50000 實施例33 化合物15 D-3 6.7 21 綠色 50000 比較例4 化合物B D-2 7.0 17 綠色 10000 實施例31-33 除了使用表2之化合物取代化合物1作為主體,且使用 ◎ 下述化合物D-3取代芳胺衍生物D-1作為摻雜物以外,與實 5施例13同様地製作有機EL元件,並評價。另外,主體與摻 雜物之比係40 : 2(膜厚比)。於表2顯示結果。 [化 60]73 200932709 [Table 2] Bulk dopant voltage (V) Luminous efficiency (cd/A) Luminescent lifetime (Hr) Example 28 Compound 13 D-2 6.5 22 Green 30000 Example 29 Compound 14 D-2 6.6 22 Green 30000 Example 30 Compound 15 D-2 6.5 22 Green 30000 Example 31 Compound 13 D-3 6.7 21 Green 50000 Example 32 Compound 14 D-3 6.7 21 Green 50000 Example 33 Compound 15 D-3 6.7 21 Green 50000 Comparison Example 4 Compound B D-2 7.0 17 Green 10000 Examples 31-33 Except that the compound of Table 2 was used instead of the compound 1 as a host, and the following compound D-3 was used instead of the arylamine derivative D-1 as a dopant An organic EL device was produced in the same manner as in Example 5 and evaluated. Further, the ratio of the host to the dopant is 40:2 (film thickness ratio). The results are shown in Table 2. [60]
10 除了使用化合物8取代化合物1作為主體,且使用下述 化合物D-2取代芳胺衍生物D-1作為摻雜物以外,與實施例 13同様地製作有機EL元件,並評價。另外,主體與推雜物 之比係40 · 2(膜厚比)。於表2顯示結果。 產業上利用之可能性 15 树明之縮合料環衍生物係有機EL元件用材料,特 74 200932709 別以作為發光材料為佳。 本發明之有機EL元件可適用於平面發光體或顯示器之 背光等光源、行動電話、PDA、衛星導航系統、車之儀表 板等顯示部、照明等。 5 於此完全引用本說明書記載之文獻内容。 [圖式簡單說明] 第1圖係本發明一實施形態之有機EL元件的概略截面 圖。 © [主要元件符號說明] 32…電洞輸送層 34…發光層 36...電子注入層 10…陽極 20…陰極 • 30··.電洞注入層10 An organic EL device was produced and evaluated in the same manner as in Example 13 except that the compound 8 was used as the host and the arylamine derivative D-1 was replaced with the following compound D-2 as a dopant. Further, the ratio of the main body to the pusher is 40 · 2 (thickness ratio). The results are shown in Table 2. Industrial Applicability 15 Shuming condensate ring derivative is a material for organic EL device, especially 74 200932709 It is preferable to use it as a light-emitting material. The organic EL device of the present invention can be applied to a light source such as a backlight of a planar light-emitting body or a display, a display unit such as a mobile phone, a PDA, a satellite navigation system, a dashboard of a car, or the like. 5 The contents of the documents described in this manual are fully quoted here. [Brief Description of the Drawings] Fig. 1 is a schematic cross-sectional view showing an organic EL device according to an embodiment of the present invention. © [Main component symbol description] 32... Hole transport layer 34...Light-emitting layer 36...Electron injection layer 10...Anode 20...Cathode • 30··. Hole injection layer
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI488941B (en) * | 2009-09-02 | 2015-06-21 | 葛來西雅帝史派有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
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EP2218706A1 (en) | 2010-08-18 |
WO2009069566A1 (en) | 2009-06-04 |
US8507106B2 (en) | 2013-08-13 |
JPWO2009069566A1 (en) | 2011-04-14 |
US20130285029A1 (en) | 2013-10-31 |
EP2218706A4 (en) | 2011-11-30 |
KR101408504B1 (en) | 2014-06-17 |
US9614159B2 (en) | 2017-04-04 |
KR20100090280A (en) | 2010-08-13 |
JP5443996B2 (en) | 2014-03-19 |
US20100320452A1 (en) | 2010-12-23 |
EP2218706B1 (en) | 2013-08-21 |
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